Surfactant‐assisted processing of polyimide/multiwall carbon nanotube nanocomposites for microelectronics applications

The dispersion and stability of carbon nanotubes (CNTs) inside a polymer matrix, especially with a high CNT content, are still big challenges. Moreover, the interaction between CNTs and the polymer matrix should be strong enough to improve the mechanical properties. The efficient dispersion of CNTs is essential for the formation of a uniform distribution of a CNT network in a polymer composite. Polyimide/multiwall CNT nanocomposites were synthesized by in situ polymerization with the aid of a surfactant. A Fourier transform infrared spectroscopy study proved that the surfactant did not hamper the polymerization of the polyimide. The microstructure, storage modulus and electrical conductivity of the nanocomposites were improved using a particular amount of the surfactant. Environmental stability test results showed that the polyimide with 1 wt% of CNTs produced with the aid of the surfactant possessed excellent reliability in high‐temperature and high‐humidity environments. Surfactants were successfully used to obtain fine‐structure polyimide/CNT nanocomposites by in situ polymerization. The enhancement of the mechanical properties was attributed to the incorporation of the surfactant. A percolation of electrical conductivity could be achieved with 1 wt% of CNTs. Copyright © 2010 Society of Chemical Industry     

Characterization and compression properties of injection molded carbon nanotube composites

Since the development of carbon nanotubes (CNTs) in 1991, they have received much attention with improved mechanical, thermal, and electrical properties of their composites compared to common polymer composites. The CNTs are currently used to increase the modulus of common thermoplastics and thermosets, including urethanes and epoxies. The CNTs are difficult to disperse within any media because of limited chemical reactivity and potential agglomeration in their “as grown” state. This study evaluated the effect of incorporating bundled and unbundled CNTs at different concentrations into Polyurethane/CNT/woven fiber reinforced composites. Optical microscopy and atomic force microscopy (AFM) characterized the dispersion of CNTs within the polymer matrix in injection molded CNT/polyurethane composites. Polyurethane/CNT/woven fiber reinforced composite plaques were prepared and then characterized by mechanical compression testing. Optical microscopy and AFM qualitatively determined a decreased agglomerate size resulting in improved mechanical properties. Results of this study show significant differences in yield stress, stress at failure, and modulus of elasticity within the various treatments. No significant differences were found for yield strain, strain at failure, and toughness. However, the conservativeness of the statistical model warrants further investigation for strain at failure and toughness with possible interaction effects of CNT concentration for each composite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Using supercritical carbon dioxide in preparing carbon nanotube nanocomposite: Improved dispersion and mechanical properties

Improvements in carbon nanotube (CNT) dispersion and subsequent mechanical properties of CNT/poly(phenylsulfone) (PPSF) composites were obtained by applying the supercritical CO₂ (scCO₂)‐aided melt‐blending technique that has been used in our laboratory for nanoclay/polymer composite preparation. The preparation process relied on rapid expansion of the CNTs followed by melt blending using a single‐screw extruder. Scanning electronic microscopy results revealed that the CNTs exposed to scCO₂ at certain pressures, temperatures, exposure time, and depressurization rates have a more dispersed structure. Microscopy results showed improved CNT dispersion in the polymer matrix and more uniform networks formed with the use of scCO₂, which indicated that CO₂‐expanded CNTs are easier to disperse into the polymer matrix during the blending procedure. The CNT/PPSF composites prepared with scCO₂‐aided melt blending and conventional melt blending showed similar tensile strength and elongation at break. The Young's modulus of the composite prepared by means of conventional direct melt blending failed to increase beyond the addition of 1 wt% CNT, but the scCO₂‐aided melt‐blending method provided continuous improvements in Young's modulus up to the addition of 7 wt% CNT. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Assessment of intertube interactions in different functionalized multiwalled carbon nanotubes incorporated in a phenoxy resin

In this work, about 1 wt% of different functionalized carbon nanotubes (CNTs), namely CNT? COOH (CNT with carboxylic groups), CNT? NH₂ (CNT with amine groups) and CNT? OH (CNT with hydroxyl groups), as well as nonfunctionalized CNTs were incorporated into a phenoxy resin via a melt mixing process. The extent of intertubes and polymer–tubes interactions and their influence on state of CNTs dispersion were assessed through determination of electrical, rheological, and morphological characteristics. CNT? NH₂ showed the lowest intertubes interactions followed by CNT? OH and CNT? COOH. Nanocomposite made from CNT? COOH showed the poorest state of CNTs dispersion and the biggest CNTs agglomerates and it remained nonconductive. The acid‐functionalized CNTs were not able to form strong polymer–tube interactions because of their high cohesive energy and therefore in the melt rheological investigations they exhibited the lowest storage modulus and complex viscosity as well as the highest loss factor among all the studied CNTs. A good balance between intertubes and polymer–tube interactions is necessary through proper selection of CNTs functional groups for achieving a good state of CNTs dispersion and consequently obtaining enhanced electrical and viscoelastic properties. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Dispersion of carbon nanotubes in ultrahigh‐molecular‐weight polyethylene by melt mixing dominated by elongation stress

A novel melt‐mixing method and corresponding mixer for polymer materials are reported. The effects of carbon nanotube (CNT) loading, rotation rate and mixing time on the morphology and properties of CNTs/ultrahigh‐molecular‐weight polyethylene (UHMWPE) nanocomposites were experimentally investigated in detail using the mixer. Homogeneous dispersion of CNTs in intractable UHMWPE is successfully realized without the aid of any additives or solvents. Differential scanning calorimetry results showed that the crystallinity increases 13.8% when 1 wt% of CNTs is added into the composites. The maximum crystallinity increased 13.5% and then decreased slightly with increasing rotation rate. The mixing time had little effect on crystallinity. Rheological tests reveal that the effect of CNT loading on the storage modulus/complex viscosity is a result of competition between the viscosity decrease due to the selective adsorption of UHMWPE onto CNT surfaces and the viscosity increase caused by the formation of an interconnected polymer–nanotube network. The storage modulus/complex viscosity decreased with increasing rotation rate/mixing time. This is a synergic result of the selective adsorption of the long molecular chains onto the CNT surface and their thermomechanical degradation. The results showed that the mixing process dominated by elongation stress is a simple, efficient green way to prepare CNTs/UHMWPE nanocomposites via melt mixing. © 2018 Society of Chemical Industry     

Mapping local microstructure and mechanical performance around carbon nanotube grafted silica fibres: methodologies for hierarchical composites

The introduction of carbon nanotubes (CNTs) modifies bulk polymer properties, depending on intrinsic quality, dispersion, alignment, interfacial chemistry and mechanical properties of the nanofiller. These effects can be exploited to enhance the matrices of conventional microscale fibre-reinforced polymer composites, by using primary reinforcing fibres grafted with CNTs. This paper presents a methodology that combines atomic force microscopy, polarised Raman spectroscopy, and nanoindentation techniques, to study the distribution, alignment and orientation of CNTs in the vicinity of epoxy-embedded micrometre-scale silica fibres, as well as, the resulting local mechanical properties of the matrix. Raman maps of key features in the CNT spectra clearly show the CNT distribution and orientation, including a 'parted' morphology associated with long grafted CNTs. The hardness and indentation modulus of the epoxy matrix were improved locally by 28% and 24%, respectively, due to the reinforcing effects of CNTs. Moreover, a slower stress relaxation was observed in the epoxy region containing CNTs, which may be due to restricted molecular mobility of the matrix. The proposed methodology is likely to be relevant to further studies of nanocomposites and hierarchical composites.     

Fabrication of high mechanical performance UHMWPE nanocomposites with high-loading multiwalled carbon nanotubes

Using conventional mixing techniques, the mechanical properties of prepared carbon nanotube (CNT)/polymer composites are not impressive enough, because of their aggregation problem at a high loading of CNTs. In this article, high mechanical performance ultrahigh molecular weight polyethylene (UHMWPE) nanocomposites with high loading of multiwalled CNTs were successfully fabricated by a new manufacturing technique. Specifically, the tensile strength and storage modulus at 25 °C of UHMWPE nanocomposites with 32 wt % of nanotubes prepared by the novel technique reaches 107.6 MPa and 6.0 GPa, respectively, about 4.7 times and 5.0 times of that of pure UHMWPE resin, which are also very high experimental results compared with polyethylene nanocomposite prepared by traditional hot-compression techniques. These attractive results suggest that the high-loading CNTs without sacrificing their dispersion and the impregnation quality of polymer-impregnated buckypapers are essential for fabricating CNTs/polymer composites with superior mechanical properties. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48667.     

Multiwalled carbon nanotube/polysulfone composites: Using the Hildebrand solubility parameter to predict dispersion

Polysulfone composites were prepared by solution casting, using various types of treated carbon nanotubes (CNTs) at loadings of up to 5 wt%. The CNT types tested were: as‐received, acid treated, OCA surfactant, OCA functionalized and Poly(methyl methacrylate) functionalized nanotubes prepared using both as‐received and acid treated CNT. The treatment types investigated were selected based upon their solubility parameters and on the results of previous studies. The treated CNTs, CNT/solvent dispersions and the final composite samples were characterised using Fourier Transform Infrared Spectroscopy (FTIR), thermal analysis, Transmission Electron Microscopy (TEM), Ultraviolet‐Visible (UV‐vis) spectroscopy, optical microscopy, electrical conductivity and tensile testing. It was observed that the all the treatments studied improved the stability of CNT in the solvent. Of the CNT types studied, composites containing OCA functionalised CNT displayed the lowest percolation threshold (3 wt%) and highest mechanical performance. While the use of Hildebrand solubility parameters is useful in indentifying promising CNT treatments, their use can not fully predict CNT dispersion behaviour and composite performance. It is also critical to consider the influence of any treatments on CNT length and residual solvent levels. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Characterizing elastic properties of carbon nanotube‐based composites by using an equivalent fiber

Effective elastic properties for carbon nanotube (CNT)‐reinforced composites are obtained through a variety of micromechanics techniques. An embedded CNT in a polymer matrix and its surrounding interphase is replaced with an equivalent fiber for predicting the mechanical properties of the CNT/polymer composite. Formulas to extract the effective material constants from solutions for the representative volume element under three loading cases are derived based on the elasticity theory. The effects of an interphase layer between the nanotubes and the polymer matrix as result of effective interphase layer are also investigated. Furthermore, this research is aimed at characterizing the elastic properties of CNTs‐reinforced composites using Eshelby–Mori–Tanaka approach based on an equivalent fiber. The variations of mechanical properties with tube radius, interphase thickness, and degree of aggregation are investigated. It is shown that the presence of aggregates has stronger impact than the interphase thickness on the effective modulus of the composite. This is because aggregates have significantly lower modulus than individual CNTs. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

Processing of yttria stabilized zirconia reinforced with multi-walled carbon nanotubes with attractive mechanical properties

The improvement of the mechanical properties of carbon nanotube reinforced polycrystalline yttria-stabilized zirconia (CNT-YSZ) was questionable in earlier investigations due to several difficulties for processing of these composites. In the present article, the authors are proposing a successful technique for mixing pre-dispersed CNTs within YSZ particles followed by a fast spark plasma sintering at relatively low temperature, resulting in near full-dense structure with well-distributed CNTs. Composites with CNT quantities ranging within 0.5-5 wt% have been analyzed and a significant improvement in mechanical properties, i.e. Young's modulus, indentation hardness and fracture toughness with respect to monolithic YSZ could be observed. To support these interesting mechanical properties, high-resolution electron microscopy and Raman spectroscopy measurements have been carried out. The analysis of densification shows that the lower densification rate of CNT reinforced composites with respect to the pure YSZ could be attributed to a slower grain boundary sliding or migration during sintering.     

Thermal properties of hyperbranched polyborate functionalized multiwall carbon nanotube/polybenzoxazine composites

Using a noncovalent functionalization strategy, hyperbranched polyborate (HBb) acts as a solubilizer for carbon nanotubes (CNTs), and a stable HBb‐CNT dispersion in N‐methyl‐pyrrolidone was produced. The thermal properties of the resulting HBb‐CNT/polybenzoxazine (B‐BOZ) composites and their carbonized structures were investigated. Scanning electron microscopy demonstrated that the fracture surface of HBb‐CNT/B‐BOZ composites was rather rough and plenty of plastic deformation was exhibited. Thermogravimetric analysis indicates an improvement in the thermal stability of the composite with CNTs, especially that of 2.0 wt% CNT modified composite. The increase in the thermal stability is due to the good nanotube dispersion and the effective polymer‐CNT interaction. Graphite‐like boron carbonitride ceramic compounds were found after the composites were carbonized at 1,100°C for 2 h, and there was more B‐C, B‐N, and C‐N bonds in the carbonized HBb‐CNT/B‐BOZ composite than that of HBb/B‐BOZ composite. The result implied that CNTs can promote the ceramic process of HBb/B‐BOZ composite, and the strategy of introducing ceramic precursor into polymer composites may be useful to improve their ablation properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Mixing of carbon nanotubes (CNTs) and aluminum powder for powder metallurgy use

In recent years, carbon nanotubes (CNTs) reinforced aluminum matrix composites (AMCs) have attracted increasing attention. The quality of dispersion, however, is a crucial factor which determines the homogeneity and final mechanical properties of these composites. This work studied the mechanical mixing methods, viz. high energy and low energy ball millings, and compared them to a novel polyester binder-assisted (PBA) mixing method. Experimental results showed that the high energy and low energy ball-milled CNTs disintegrated and there were residual stresses, unlike the PBA-CNTs. The CNT dispersion conditions by these three methods were discussed. The Al-CNTs mixture was subsequently consolidated by powder metallurgy (PM) technique. Small addition of CNTs (0.5 wt.%) evidently improved the tensile strength and hardness of the composite by comparing with the pure matrix. Mechanical property enhancements of the Al-0.5CNT composites from PBA and high energy ball milling were superior to that mixed by low energy ball milling. This showed good dispersion effect in PBA and high energy ball milling technique.     

碳纳米管预处理方法对天然橡胶/纯化碳纳米管复合材料力学性能的影响

纯化后的碳纳米管(CNT)分别经过球磨、表面活性剂十二烷基苯磺酸钠或分散-黏合体系预处理,再与100份(质量)天然橡胶(NR)混炼,可制备NR/纯化CNT复合材料。结果表明,纯化CNT直接与NR混炼,前者在NR中的分散效果不好,二者的界面结合欠佳。纯化CNT经球磨后,团聚程度增加,对复合材料力学性能影响不大。经表面活性剂十二烷基苯磺酸钠处理后的纯化CNT,内聚能下降,用差示扫描量热法(DSC)测定复合材料的DSC曲线表明,复合材料的结晶熔融峰面积增大,力学性能降低。用分散-黏合体系处理纯化CNT,可同时提高纯化CNT在橡胶中的分散效果及界面黏合性,试样结晶熔融峰变得不明显,因此该复合材料的邵尔A型硬度提高,拉伸强度、300％定伸应力和撕裂强度等优于其他试样。     

Improved mechanical properties of carbon nanotube/polymer composites through the use of carboxyl-epoxide functional group linkages

Single-walled and multi-walled carbon nanotubes (CNTs) were functionalized with carboxyl groups and dispersed in a polymer containing an epoxide group. We have then observed experimentally that mutual chemical reaction between the functional groups on the CNTs with the polymer epoxide group can enhance, two-fold, both the tensile strength and elastic modulus, E, of single walled CNT/polymer composites. A simple model was formulated to understand the variation of E with CNT volume fraction, considering agglomeration effects as well. An increase in the work of fracture, obtained from the experimental stress-strain curves, was seen at low nanotube filling fractions and is presumably due to crack bridging of the polymer matrix by CNTs. The influence of CNT length and geometry on mechanical properties, along with the influences of electrical and mechanical percolation thresholds was considered.     

Molecular dynamics simulation of mechanical properties and interaction energy of polythiophene/polyethylene/poly(p‐phenylenevinylene) and CNTs composites

Carbon nanotubes (CNTs) have very important applications in ultrastrong lightweight materials. CNTs can improve mechanical properties of polymer matrix such as breaking stress and Young's modulus. In this article, we studied the interaction between polythiophene (PT)/polyethylene (PE)/poly(p‐phenylenevinylene) (PPV) and CNTs by molecular dynamics (MD) simulation based on a reactive force field (ReaxFF). We studied the influence of CNT diameter, polymer type, and temperature on interaction energy. We found that a large radius CNT at low temperature shows the strongest interaction energy with PT. In addition, we computed the mechanical properties of CNTs‐polymer composites such as the breaking stress, breaking strain, and Young's modulus. Our results show that there is a direct relation between mechanical properties and interaction energy. We found that the mechanical properties of CNTs‐PT composite are better than CNTs‐PPV and CNTs‐PE and it is a good candidate for ultrastrong lightweight materials. We studied the influence of temperature on the mechanical properties. Our results show that CNTs‐polymer composites show stronger mechanical properties at low temperature. We found that ReaxFF can reproduce the other force fields results and it is a very powerful force field to study the various properties of CNTs‐polymer composites. POLYM. COMPOS., 35:2261–2268, 2014. © 2014 Society of Plastics Engineers     

Alignment and properties of carbon nanotube buckypaper/liquid crystalline polymer composites

Carbon nanotubes (CNTs) have been recognized as a potential superior reinforcement for high‐performance, multifunctional composites. However, non‐uniform CNT dispersion within the polymer matrix, the lack of adequate adhesion between the constituents of the composites, and lack of nanotube alignment have hindered significant improvements in composite performance. In this study, we present the development of a layer‐by‐layer assembly method to produce high mechanical performance and electrical conductivity CNT‐reinforced liquid crystalline polymer (LCP) composites using CNT sheets or buckypaper (BP) and self‐reinforcing polyphenylene resin, Parmax. The Parmax/BP composite morphology, X‐ray diffraction, mechanical, thermal, and electrical properties have been investigated. SEM observations and X‐ray diffraction demonstrate alignment of the CNTs due to flow‐induced orientational ordering of LCP chains. The tensile strength and Young's modulus of the Parmax/BP nanocomposites with 6.23 wt % multi‐walled carbon nanotube content were 390 MPa and 33 GPa, respectively, which were substantially improved when compared to the neat LCP. Noticeable improvements in the thermal stability and glass transition temperature with increasing CNT content due to the restriction in chain mobility imposed by the CNTs was demonstrated. Moreover, the electrical conductivity of the composites increased sharply to 100.23 S/cm (from approximately 10^?13 S/cm) with the addition of CNT BP. These results suggest that the developed approach would be an effective method to fabricate high‐performance, multifunctional CNT/LCP nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

In situ preparation of polyimide/amino‐functionalized carbon nanotube composites and their properties

In order to improve the dispersion of carbon nanotubes (CNTs) in polyimide (PI) matrix and the interfacial interaction between CNTs and PI, 4,4′‐diaminodiphenyl ether (ODA)‐functionalized carbon nanotubes (CNTs‐ODA) were synthesized by oxidation and amidation reactions. The structures and morphologies of CNTs‐ODA were characterized using Fourier transform infrared spectrometer, transmission electron microscopy, and thermal gravimetric analysis. Then a series of polyimide/amino‐functionalized carbon nanotube (PI/CNT‐ODA) nanocomposites were prepared by in situ polymerization. CNTs‐ODA were homogeneously dispersed in PI matrix. The influence of CNT‐ODA content on mechanical properties of PI/CNT‐ODA nanocomposites was investigated. It was found that the mechanical properties of nanocomposites were enhanced with the increase in CNT‐ODA loading. When the content of CNTs‐ODA was 3 wt%, the tensile strength of PI/CNT‐ODA nanocomposites was up to 169.07 MPa (87.11% higher than that of neat PI). The modulus of PI/CNTs‐ODA was increased by 62.64%, while elongation at break was increased by 66.05%. The improvement of the mechanical properties of PI/CNT‐ODA nanocomposites were due to the strong chemical bond and interfacial interaction between CNTs‐ODA and PI matrix. POLYM. COMPOS., 35:1952–1959, 2014. © 2014 Society of Plastics Engineers     

Effects of surface modification on rheological and mechanical properties of CNT/epoxy composites

Despite superior properties of carbon nanotubes (CNTs), physical properties of the CNT/epoxy composites are not improved significantly because interfacial bonding between the CNTs and the polymer matrix is weak. CNTs were treated by an acidic solution to remove impurities and modified subsequently by amine treatment or plasma oxidation to improve interfacial bonding and dispersion of nanotubes in the epoxy matrix. The functional groups on the surface of treated CNTs were investigated by X-ray photoelectron spectroscopy. The surface modified CNTs were embedded in the epoxy resin by ultra-sonication and the cured nanotube containing composites were characterized by field emission scanning electron microscopy. Rheological properties of nanotube containing epoxy resin and mechanical properties of the modified CNT/epoxy composites were improved because the modification of CNTs improved dispersion and interaction between the CNT and the epoxy resin.     

Hotmelts with improved properties by integration of carbon nanotubes

With the aim of the development of conductive and mechanically improved adhesives, carbon nanotubes (CNTs) were dispersed by melt mixing into a non-reactive polyolefine based hotmelt adhesive. The composite materials, containing 0.5 to 5.0 wt% multi-walled CNTs (MWNTs), showed electrical percolation at about 0.75 wt%. Investigations of the mechanical properties using tensile tests resulted in a significant enhancement of Young's modulus up to 372% and nearly doubling of tensile strength at 5.0 wt%. Even if the hotmelt material is highly elastic compared to typical thermoplastic matrices, the melt mixing resulted in suitable CNT dispersion. The melt viscosity increased with CNT loading, however near the observed electrical percolation threshold the processability was not notably reduced. Most important, next to conductivity at low CNT loadings, also a significant enhancement in the shear strength of bonded joints of AlMg3 up to values of 250% of the pure hotmelt could be obtained. The property profile can be tailored with CNT concentration, indicating the suitability of CNT addition into these hotmelt adhesives.     

Different filler effect of carbon nanotube and graphene nanoplatelet in the poly(arylene ether nitrile) matrix

The different filler effects of identical nitrile‐functionalized carbon nanotubes (CNTs) and graphene nanoplatelets (GNs) in a poly(arylene ether nitrile) (PEEN) matrix were investigated. PEEN/CNT and PEEN/GN composites were prepared by a facile solution‐casting method and systematically investigated for their differences in morphological, thermal and rheological properties. In the PEEN matrix GNs contact one another in a plane‐to‐plane manner, while CNTs are separated. Compared with PEEN/CNT composites, PEEN/GN composites below 2 wt% filler content exhibited higher thermal stability. Rheological properties of the resulting composites indicated that PEEN/GN composites were more sensitive to strain and exhibited higher η*, G′ and G″ than PEEN/CNT composites. The rheological percolation for CNTs is over 2 wt%, higher than that for GNs (around 1 wt%). All these differences originate from the different dimensions and structures of CNTs and GNs: GNs with a flake‐like structure and larger surface area can have stronger physical and interfacial interactions with the polymer matrix. This work gives a comparative view of the different filler effects that functionalized CNTs and GNs can have in the polymer host. With identical processing technology, GNs can show a stronger filler effect than CNTs. © 2012 Society of Chemical Industry