Influence of different carbon nanotubes on the electrical and mechanical properties of melt mixed poly(ether sulfone)-multi walled carbon nanotube composites

Commercial Udel® poly(ether sulfone) (PSU) was filled with three different commercially available multiwalled carbon nanotubes (MWCNTs) by small scale melt mixing. The MWCNTs were as grown NC 7000 and two of its derivatives prepared by ball milling treatment. One of them was unmodified (NC 3150); the other was amino modified (NC 3152). The main difference beside the reactivity was the reduced aspect ratio of NC 3150 and NC 3152 caused by ball milling process. All PSU/MWCNT composites with similar filler content were prepared under fixed processing conditions and comparative analysis of their electrical and mechanical properties were performed and were correlated with their microstructure, characterized by optical microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A non-uniform MWCNT dispersion was observed in all composites. The MWCNTs were present in form of agglomerates in the size of 10–60 μm whereas the deagglomerated part was homogeneously distributed in the PSU matrix. The differences in the agglomeration states correlate with the variations of properties between different PSU/MWCNT composites. The lowest electrical percolation threshold of 0.25–0.5 wt.% was observed for the shortened non-functionalized MWCNT composites and the highest for amine-modified MWCNT composites (ca. 1.5 wt.%). The tensile behavior of the three composites was only slightly altered with CNT loading as compared to the pure PSU. However, the elongation at break showed a reduction with MWCNT loading and the reduction was least for composite with best MWCNT dispersion.     

The poly(urethane-ionic liquid)/multi-walled carbon nanotubes composites

In the paper, a novel kind of imidazolium based poly(urethane-ionic liquid)/multi-walled carbon nanotubes (PUIL/MWCNT) composites was facilely prepared by uncovalent ways. The imidazolium based ionic liquid (IL) greatly improved the dispersion of pristine MWCNTs in PUIL by the π-cation interaction formed between the imidazolium cation and the π-electron of MWCNTs. The PUIL/MWCNT composites showed obviously increased modulus, glass transition temperature and tensile strength in comparison with PU/MWCNT composites. The thermal and mechanical properties of the PUIL/MWCNT composites presented significant increase with low load of the MWCNTs. It indicated the interactions between PUIL and MWCNTs played an important role to enhance the performances of the composites.     

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。     

RTM processing and electrical performance of carbon nanotube modified epoxy/fibre composites

This investigation focuses on nanoparticle filtration in the processing of multiscale carbon and glass fibre composites via resin transfer moulding. Surface modified and unmodified carbon nanotubes (CNTs) were incorporated into a commercial epoxy resin. The dispersion quality was evaluated using electrical measurements of the liquid suspensions. The manufacturing process was adapted to the challenges posed by the modified rheological behaviour of the CNT loaded resin. Nanoparticle filtration was observed; with some of the unmodified systems following so called ‘cake filtration’ behaviour. This resulted in nonlinear flow behaviour that deviated from the ideal response observed in RTM filling in conventional composites. The electrical conductivity of relatively high fibre volume fraction multiscale carbon and glass laminates increased by less than an order of magnitude with the addition of the nanotubes.     

Electric field effects on CNTs/vinyl ester suspensions and the resulting electrical and thermal composite properties

In this study, electrical conductivity of a vinyl ester based composite containing low content (0.05, 0.1 and 0.3 wt.%) of double and multi-walled carbon nanotubes with and without amine functional groups (DWCNTs, MWCNTs, DWCNT-NH₂ and MWCNT-NH₂) was investigated. The composite with pristine MWCNTs was found to exhibit the highest electrical conductivity. Experiments aimed to induce an aligned conductive network with application of an alternating current (AC) electric field during cure were carried out on the resin suspensions with MWCNTs. Formation of electric anisotropy within the composite was verified. Light microscopy (LM), scanning electron (SEM) and transmission electron microscopy (TEM) were conducted to visualize dispersion state and the extent of alignment of MWCNTs within the polymer cured with and without application of the electric field. To gain a better understanding of electric field induced effects, glass transition temperature (T_g) of the composites was measured via Differential Scanning Calorimetry (DSC). It was determined that at 0.05 wt.% loading rate of MWCNTs, the composites, cured with application of the AC electric field, possessed a higher T_g than the composites cured without application of the AC electric field.     

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.     

Percolation behaviour of multiwalled carbon nanotubes of altered length and primary agglomerate morphology in melt mixed isotactic polypropylene-based composites

The effect of ball milling on the structural characteristics and further on the dispersion and percolation behaviour of multiwalled carbon nanotubes (MWCNTs) in melt mixed composites using a maleic anhydride modified isotactic polypropylene as matrix was investigated. TEM and SEM revealed that ball milled nanotubes were considerably shorter and showed a compact primary agglomerate morphology compared to the as-synthesised MWCNTs. At macro scale ball milled MWCNTs were found to be better dispersed, whereas at sub-micron scale the states of dispersion of both nanotube materials were comparable. The differences in the composite morphologies as well as in the composites electrical and rheological percolation behaviour were assigned to the altered MWCNT structure due to ball milling treatment. The dispersibility of ball milled MWCNTs was restricted due to their more compact agglomerate morphology. Furthermore, the ability to form percolated network structures was restrained by their shorter length and, again, their compact primary agglomerates. An effective agglomerate interaction radius depending on the nanotube structural characteristics, length and agglomerate morphology, is suggested in order to explain the experimental findings.     

酸化处理多壁碳纳米管/氰酸酯树脂复合材料性能

采用酸化处理的多壁碳纳米管（MWCNTs）增强双酚A型氰酸酯-酚醛型氰酸酯（BCE-NCE）树脂。通过SEM、TEM对MWCNTs/BCE-NCE树脂复合材料微观结构进行表征,利用DSC、DMA和TG/DTA对MWCNTs/BCE-NCE树脂复合材料热性能进行研究,采用电子拉力机对MWCNTs/BCE-NCE树脂复合材料力学性能进行测试,采用谐振腔法对MWCNTs/BCE-NCE树脂复合材料介电性能进行测试。结果表明,混酸处理过的MWCNTs在BCE-NCE树脂基体中的分散效果较好。MWCNTs对BCE-NCE树脂热力学性能影响不大,当MWCNTs添加量为0.8wt%时,BCE-NCE树脂玻璃化转变温度（T_g）从298℃下降到285℃,但仍维持较高水平。当MWCNTs添加量为0.6wt%时,MWCNTs/BCE-NCE树脂复合材料冲击强度为11.40 kJ/m²,提高了40.7%。MWCNTs的加入增加了BCE-NCE树脂介电常数和介电损耗,当MWCNTs添加量为0.8wt%、频率为1 GHz时,MWCNTs/BCE-NCE树脂复合材料介电常数为5.1,介电损耗为0.032。因此,MWCNTs/BCE-NCE树脂复合材料未来可在耐高温复合材料和电子等行业应用。     

Dispersions of carbon nanotubes/polyhedral oligomeric silsesquioxanes hybrids in polymer: the mechanical,electrical and EMI shielding properties

A hybrid was synthesized by grafting polyhedral oligomeric silsesquioxane (POSS) to multiwalled carbon nanotubes (MWCNTs). The MWCNT/polymer composites produced using silsesquioxane grafted MWCNTs as a filler had a high electromagnetic interference shielding effectiveness. Homogeneous dispersion of silsesquioxane grafted MWCNTs occurred throughout the polymer without any aggregation, while a pristine MWCNT aggregate that integrated several nanotube domains existed in the polymer matrix. A comparative study of the optical transmittance, electrical, and electromagnetic interference shielding properties of poly(l-lactide) (PLLA)/MWCNT composites based on pristine MWCNTs and silsesquioxane grafted MWCNTs was carried out. A high electromagnetic interference shielding effectiveness (15–16 dB) was obtained in the 36–50 GHz range at a relatively low filler loading (4 wt%) in the PLLA/silsesquioxane grafted MWCNT composite.     

Development of conducting polychloroprene rubber using imidazolium based ionic liquid modified multi-walled carbon nanotubes

A simplified and an eco-friendly approach to develop polychloroprene rubber composites with high electrical conductivity is reported. The usage of room temperature ionic liquid, 1-butyl 3-methyl imidazolium bis(trifluoromethylsulphonyl)imide and a low concentration (5 phr) of commercial grade multi-walled carbon nanotubes (MWCNTs) in polychloroprene rubber exhibited an electrical conductivity of 0.1 S/cm with a stretchability >500%. The physical (cation-pi/pi-pi) interaction between the ionic liquid and the MWCNTs is evidenced by Raman spectroscopy. Transmission electron microscopy images exhibit an improved dispersion of the BMI modified tubes in matrix at various magnification scales. The dependency of dynamic properties on the concentration of ionic liquid at constant loading of nanotubes supports the fact that ionic liquid assists in the formation of filler-filler networks. The tensile modulus of 3 phr loaded modified MWCNT/CR composite is increased by 50% with regard to that of the unmodified MWCNT/CR composite. Mooney-Rivlin plot displays the existence of rubber-filler interactions.     

多壁碳纳米管的辐照处理及其对多壁碳纳米管/环氧树脂复合材料热性能的影响

在空气中用高频高压电子加速器辐照多壁碳纳米管(MWCNTs),采用红外光谱、能谱分析、拉曼光谱和透射电镜表征分析辐照处理对碳纳米管结构的影响;通过原位复合法制备MWCNT/环氧树脂(EP)复合材料.采用场发射扫描电镜、热失重分析和动态力学分析研究辐照处理MWCNTs对环氧树脂热稳定性的影响.结果表明:电子束辐照处理使MWCNTs表面接入了少量的含氧基团,同时破坏了MWCNTs的完整结构,当辐照剂量为170 kGy时,接枝含氧基团的量最多(约为4％),且结构破坏程度较小.与原始MWCNT/EP体系相比,经电子束辐照处理后的MWCNTs在EP中分散得更均匀,并能使材料的最大热分解温度和玻璃化转变温度较纯EP有所提高,在EP中加入质量分数0.5％的经170kGy辐照处理后的MWCNTs,能够使材料的最大热分解温度和玻璃化转变温度分别提高约14℃和8℃.     

Fracture mechanisms of epoxy filled with ozone functionalized multi-wall carbon nanotubes

This work focused on the fracture mechanisms and reinforcing effects of ozone-treated multi-walled carbon nanotubes (MWCNTs) in epoxy matrix. Ozone functionalization of MWCNTs was found to be of help for a better dispersion and stronger interfacial bonding with epoxy matrix, which in turn improve the strength and fracture toughness of the resin. The MWCNT/epoxy composites showed complicated failure modes than the conventional fibrous composites, which have been quantitatively investigated and correlated with the fracture toughness of the nanocomposites studied.     

Rubber composites based on graphene nanoplatelets,expanded graphite,carbon nanotubes and their combination: A comparative study

Solution styrene butadiene rubber (S-SBR) composites reinforced with graphene nanoplatelets (GnPs), expanded graphite (EG), and multiwalled carbon nanotubes (MWCNTs) were prepared and the electrical and various mechanical properties were compared to understand the specific dispersion and reinforcement behaviours of these nanostructured fillers. The electrical resistivity of the rubber composite gradually decreased with the increase of filler amount in the composite. The electrical percolation behaviour was found to be started at 15 phr (parts per hundred rubber) for GnP and 20 phr for EG filled systems, whereas a sharp drop was found at 5 phr for MWCNT based composites. At a particular filler loading, dynamic mechanical analysis and tensile test showed a significant improvement of the mechanical properties of the composites comprised of MWCNT followed by GnP and then EG. The high aspect ratio of MWCNT enabled to form a network at low filler loading and, consequently, a good reinforcement effect was observed. To investigate the effect of hybrid fillers, MWCNT (up to 5 phr) were added in a selected composition of EG based compounds. The formation of a mixed filler network showed a synergistic effect on the improvement of electrical as well as various mechanical properties.     

Poly(3- hydroxybutyrate)/Bioglass(®) composite films containing carbon nanotubes

Poly(3hydroxybutyrate) (P(3HB))/Bioglass(?)?composites incorporating multiwalled carbon nanotubes (MWCNTs) have been successfully prepared by the solvent casting technique. The microstructure, electrical properties and bioactivity of the composites were characterized using scanning electron microscopy, x-ray diffraction and current-voltage measurements. Different concentrations of MWCNTs were used to determine their effect on the electrical properties of the composites. MWCNTs and Bioglass(?) particles were found to be homogeneously dispersed throughout the P(3HB) matrix. The electrical resistance of the composite samples decreased on increasing the MWCNT concentration, as expected. An in vitro degradation study in simulated body fluid (SBF) was carried out on composite samples. The formation of hydroxyapatite on the surfaces of P(3HB)/Bioglass(?)/MWCNT composite films was confirmed after two months of immersion in SBF. This hydroxyapatite layer was not formed on the neat polymeric films and on composites containing MWCNTs only (without Bioglass(?)). It was found that the presence of MWCNTs did not hinder the bioactivity of the Bioglass(?) particles, as confirmed by SEM and XRD studies on composite samples.     

The effect of multiwall carbon nanotubes on the in-plane shear behavior of epoxy glass fiber reinforced composites

In this study, we investigate how multi-wall carbon nanotubes (MWCNTs) affect the in-plane shear mechanical behavior of glass fiber/epoxy composite. These multi-scale composites are fabricated using vacuum infusion: pristine MWCNT and amino-functionalized MWCNT are incorporated into epoxy resins at concentrations of both 0.1 and 0.3 wt.% and are subsequently evaluated. The MWCNT are mixed into the resins by mechanical stirring and sonication prior to resin infusion, and the MWCNT distribution in the cured laminate is then evaluated by performing a heat conduction assessment. Monotonic and cyclic quasi-static room temperature in-plane shear tests are performed following the ASTM D 4255 standard. The initial shear modulus, the deterioration of the shear modulus during plastic deformation and material hardening are evaluated. Incorporating MWCNT into the resins did not affect the parameters investigated under the imposed conditions.     

Aligning carbon nanotubes using bulk acoustic waves to reinforce polymer composites

Bulk acoustic waves (BAWs) are used to align multi-walled carbon nanotubes (MWCNTs) in polymer composite materials. MWCNTs are first dispersed in the liquid state of a thermoset resin and aligned using standing BAWs. Cross-linking of the resin fixates the aligned MWCNTs in the polymer matrix material. We have quantified the alignment obtained with this method on the macro, micro, and nanoscale, and it is found to be similar to other alignment techniques such as stretching, slicing, and wet spinning. The elastic modulus and ultimate tensile strength of composite material specimens with aligned MWCNTs, fabricated using this technique, are evaluated and compared with specimens consisting of randomly oriented MWCNTs and resin material without MWCNTs. Different MWCNT loading rates are considered. The elastic modulus of composite material specimens with only 0.15 weight percent aligned MWCNTs is observed to be 44% higher than specimens with randomly oriented MWCNTs, and 51% higher than specimens without MWCNTs. However, further increasing the MWCNT loading rate does not significantly increase the elastic modulus and ultimate tensile strength, likely because of insufficient dispersion of MWCNTs in the thermoset matrix material.     

Hybrid Composite Using Natural Filler and Multi-Walled Carbon Nanotubes (MWCNTs)

This paper presents an experimental study on the development of hybrid composites comprising of multi-walled carbon nanotubes (MWCNTs) and natural filler (oil palm shell (OPS) powder) within unsaturated polyester (UP) matrix. The results revealed that the dispersion of pristine MWCNTs in the polymer matrix was strongly enhanced through use of the solvent mixing method assisted by ultrasonication. Four different solvents were investigated, namely, ethanol, methanol, styrene and acetone. The best compatibility with minimum side effects on the curing of the polyester resin was exhibited by the styrene solvent and this produced the maximum tensile and flexural properties of the resulting nanocomposites. A relatively small amount of pristine MWCNTs well dispersed within the natural filler polyester composite was found to be capable of improving mechanical properties of hybrid composite. However, increasing the MWCNT amount resulted in increased void content within the matrix due to an associated rapid increase in viscosity of the mixture during processing. Due to this phenomenon, the maximum tensile and flexural strengths of the hybrid composites were achieved at MWCNT contents of 0.2 to 0.4 phr and then declined for higher MWCNT amounts. The flexural modulus also experienced its peak at 0.4 phr MWCNT content whereas the tensile modulus exhibited a general decrease with increasing MWCNT content. Thermal stability analysis using TGA under an oxidative atmosphere showed that adding MWCNTs shifted the endset degradation temperature of the hybrid composite to a higher temperature.     

Effects of stretching on mechanical properties of aligned multi-walled carbon nanotube/epoxy composites

Composites based on epoxy resin and differently aligned multi-walled carbon nanotube (MWCNT) sheets have been developed using hot-melt prepreg processing. Aligned MWCNT sheets were produced from MWCNT arrays using the drawing and winding technique. Wavy MWCNTs in the sheets have limited reinforcement efficiency in the composites. Therefore, mechanical stretching of the MWCNT sheets and their prepregs was conducted for this study. Mechanical stretching of the MWCNT sheets and hot stretching of the MWCNT/epoxy prepregs markedly improved the mechanical properties of the composites. The improved mechanical properties of stretched composites derived from the increased MWCNT volume fraction and the reduced MWCNT waviness caused by stretching. With a 3% stretch ratio, the MWCNT/epoxy composites achieved their best mechanical properties in this study. Although hot stretching of the prepregs increased the tensile strength and modulus of the composites considerably, its efficiency was lower than that of stretching the MWCNT sheets.     

Influence of raw carbon nanotubes diameter for the optimization of the load composition ratio in epoxy amperometric composite sensors

In this work, it is reported the necessity to characterize the raw carbon materials before their application in composite electrodes based on multiwall carbon nanotubes (MWCNTs) dispersed in epoxy resin for the development of improved amperometric sensors. These sensors must contain an optimum MWCNT/epoxy ratio for their best electroanalytical response. The main drawback in MWCNTs composite materials resides in the lack of homogeneity of the different commercial nanotubes largely due to different impurities content, as well as dispersion in their diameter/length ratio and state of aggregation. The optimal composite electrode composition takes into account the high electrode sensitivity, low limit of detection, fast response, and electroanalytical reproducibility. These features depend on carbon nanotube physical properties as the diameter. Three different commercial carbon nanotubes with different diameters were characterized by transmission electron microscopy and the results were significantly different from the ones provided by the manufacturers. Then, the three MWCNTs were used for the MWCNT/epoxy sensors construction. After an accurate electrochemical characterization by cyclic voltammetry and electrochemical impedance spectroscopy, they were employed as working electrodes using ascorbic acid as a reference analyte. Percolation theory was applied in order to verify the electrochemical results. It is demonstrated that the optimum interval load of raw carbon material in the optimized-composite electrodes closely depends on the MWCNTs diameter, needing 5 % in carbon content for the narrowest MWCNTs containing composite electrodes versus 12 % for the widest MWCNTs.     

Electrical properties of multiwalled carbon nanotube reinforced fused silica composites

Multiwalled carbon nanotube (MWCNT)-fused silica composite powders were synthesized by solgel method and dense bulk composites were successfully fabricated via hot-pressing. This composite was characterized by XRD, HRTEM, and FESEM. MWCNTs in the hot-pressed composites are in their integrity observed by HRTEM. The electrical properties of MWCNT-fused silica composites were measured and analyzed. The electrical resistivity was found to decrease with the increase in the amount of the MWCNT loading in the composite. When the volume percentage of the MWCNTs increased to 5 vol%, the electrical resistivity of the composite is 24.99 omega cm, which is a decrease of twelve orders of value over that of pure fused silica matrix. The electrical resistivity further decreases to 1.742 omega. cm as the concentration of the MWCNTs increased to 10 vol%. The dielectric properties of the composites were also measured at the frequency ranging from 12.4 to 17.8 GHz (Ku band) at room temperature. The experimental results reveal that the dielectric properties are extremely sensitive to the volume percentage of the MWCNTs, and the permittivities, especially the imaginary permittivities, increase dramatically with the increase in the concentration of the MWCNTs. The improvement of dielectric properties in high frequency region mainly originates from the greatly increasing electrical properties of the composite.