High‐Performance UV Protective Waterborne Polymer Coatings Based on Hybrid Graphene/Carbon Nanotube Radicals Scavenging Filler

Ultraviolet (UV) degradation is one of the most important challenges of waterborne coatings in exterior applications. One of the ways to address this issue is addition of radical scavenging species within the polymer matrix. Herein, hybrids of graphene (G) and multiwall carbon nanotubes (CNTs) in different ratios are used as radical scavenging species. Evaluated by electron paramagnetic resonance spectroscopy, it is found that the hybrid made of G/CNTs in ratio of 10:1 efficiently captures and quenches the free radicals. The waterborne polymer composites containing 1 wt% of hybrid G/CNT are synthesized by in situ miniemulsion free radical polymerization using a water soluble initiator. However, due to excellent efficiency to capture free radicals, the polymerization performed using water soluble initiators in the presence of 10:1 G/CNT filler is hindered. This is resolved by physical separation of the free radicals and the scavenging materials within different phases by use of oil soluble initiator. The resulting polymer composites, beside having excellent mechanical resistance, present exceptional stability under accelerated aging conditions during 400 h, suppressing almost completely the UV photodegradation. This is attributed to the efficient radical scavenging of the G/CNTs hybrid filler distributed within polymer matrix, resulting in high‐performance UV protective waterborne composite coatings.     

Enhanced interfacial strength of carbon nanotube/copper nanocomposites via Ni-coating: Molecular-dynamics insights

The molecular bridging between carbon nanotube (CNT) within the meta matrix is hopeful for enhancing nanocomposite's mechanical performance. One of the main problems for nanocomposites is the inadequate bonding between nonstructural reinforcement and meta matrix. Ni-coating on CNT is an effective method to overcome the drawback of the inadequate strength, but the enhancing mechanism has not well interpreted yet. In this paper, the enhancing mechanism will be interpreted from the molecular-dynamics insights. The pullout process of CNT and Ni-coated CNT against copper matrix is investigated. The effects of geometric parameters, including CNT length and diameter, are taken into considerations and discussed. Results show that the interfacial strength is significantly improved after the Ni-coated CNT, which shows a good agreement with the experimental results available in the open literature. Besides, the sliding mechanism of Ni-coated CNTs against copper matrix is much more like a kind of friction sliding and directly related to the embedded zone. However, the pullout force of the CNT without Ni-coating is nearly proportional to its diameter, but independent of embedded length.     

High Rate and Long Cycle Life of a CNT/rGO/Si Nanoparticle Composite Anode for Lithium‐Ion Batteries

Si nanoparticle (Si‐NP) composite anode with high rate and long cycle life is an attractive anode material for lithium‐ion battery (LIB) in hybrid electric vehicle (HEV)/pure electric vehicle (PEV). In this work, a carbon nanotube (CNT)/reduced graphene oxide (rGO)/Si nanoparticle composite with alternated structure as Li‐ion battery anode is prepared. In this structure, rGO completely wraps the entire Si/CNT networks by different layers and CNT networks provide fast electron transport pathways with reduced solid‐state diffusion, so that the stable solid‐electrolyte interphase layer can form on the whole surface of the matrix instead of on single Si nanoparticle, which ensure the high cycle stability to achieve the excellent cycle performance. As a result, the CNT/rGO/Si‐NP anode exhibits high performances with long cycle life (≈455 mAh g^?1 at 15 A g^?1 after 2000 cycles), high specific charge capacity (≈2250 mAh g^?1 at 0.2 A g^?1, ≈650 mAh g^?1 at 15 A g^?1), and fast charge/discharge rates (up to 16 A g^?1). This nanostructure anode with facile and low‐cost synthesis method, as well as excellent electrochemical performances, makes it attractive for the long life cycles at high rate of the next generation LIB applications in HEV/PEV.     

Carbon nanotube (CNT)–epoxy nanocomposites: a systematic investigation of CNT dispersion

A systematic investigation of the dispersion of carbon nanotubes (CNTs), 1–6 nm in diameter and a few microns in length, in a bisphenol F-based epoxy resin has been presented. Several dispersing techniques including high-speed dissolver, ultrasonic bath/horn, 3-roll mill, etc. have been employed. Optical microscopy has been extensively used to systematically characterise the state of CNT dispersion in the epoxy resin during the entire processing cycle from mixing CNT with resin to adding and curing with hardener. Complimentary viscosity measurements were also performed at various stages of nanocomposite processing. A method to produce a good CNT dispersion in resin was established, but the state of CNT dispersion was found to be extremely sensitive to its physical and chemical environments. The cured nanocomposites were further tested for their thermo-mechanical properties by dynamic mechanical thermal analysis (DMTA), and for flexural and compressive mechanical properties. The measured properties of various nanocomposite plates were then discussed in view of the corresponding CNT dispersion.     

Multiscale modeling of graphene- and nanotube-based reinforced polymer nanocomposites

A combination of molecular dynamics, molecular structural mechanics, and finite element method is employed to compute the elastic constants of a polymeric nanocomposite embedded with graphene sheets, and carbon nanotubes. The model is first applied to study the effect of inclusion of graphene sheets on the Young modulus of the composite. To explore the significance of the nanofiller geometry, the elastic constants of nanotube-based and graphene-based polymer composites are computed under identical conditions. The reinforcement role of these nanofillers is also investigated in transverse directions. Moreover, the dependence of the nanocomposite?s axial Young modulus on the presence of ripples on the surface of the embedded graphene sheets, due to thermal fluctuations, is examined via MD simulations. Finally, we have also studied the effect of sliding motion of graphene layers on the elastic constants of the nanocomposite.     

Improving the thermal properties of fluoroelastomer (Viton GF-600S) using carbon nanotube

Nanocomposites were prepared using carbon nanotubes (CNTs) in the formulations of fluoroelastomer (FE). Thermogravimetric analysis (TGA) results revealed that CNT improved the thermal properties of FE, resulting in higher amount of FE and char remaining within the temperature range of 520–900 °C, relative to unfilled FE and carbon black (CB)-filled FE. The same results also revealed that more percentage of FE was undegraded or less degraded especially near CNT. Energy dispersive X-ray (EDX) results indicated that the percentage of carbon and fluorine in the residue of TGA scans up to 560 °C of CNT-filled FE (CNT/FE) were higher compared to the CB-filled FE (CB/FE), and CB/FE was higher than FE. EDX results of TGA residue (run up to 900 °C) showed that most of the undegraded FE which was not degraded at temperatures below 560 °C was degraded from 560 °C to 900 °C in both CNT/FE and CB/FE, with the char in CNT/FE being more than that in CB/FE. Residue of samples after TGA scans up to 900 °C indicated that, Zn did not undergo any reaction with CNT in the CNT/FE. In CB/FE, some percentage of ZnO reacted with carbon. EDX analysis of thermal aged specimens under air showed that with increasing aging time, more percentage of C, O, and F were lost from the surface of filler/FE and FE. The order of element loss is: CNT/FE < FE < CB/FE.     

Influence of functionalization on mechanical and electrical properties of carbon nanotube-based silver composites

In this study, we have extended the molecular-level mixing method to fabricate multiwall carbon nanotube (CNT)-reinforced silver nanocomposites. The multiwall nanotubes used in the synthesis process were dispersed by two ways viz. covalent and non-covalent functionalization techniques. To elucidate the comparative effects of functionalization, structural, mechanical and electrical properties of nanocomposites were evaluated before and after sintering. The structural characterization revealed that the nanotubes were embedded, anchored and homogenously dispersed within the silver matrix. Hardness and Young’s modulus of nanotube-reinforced nanocomposite were increased by a factor of 1–1.6 times than that of pure silver, even before and after the sintering. Covalently functionalized nanotube-based composites have shown more enhanced mechanical properties. The CNT reinforcement also improved the electrical conductivity of low-conducting nanosilver matrix before sintering. Non-covalently functionalized nanotube-based nanosilver composites showed more increased electrical conductivity before sintering. But a negative reinforcement effect was observed in high-conducting bulk silver matrix after the sintering. Thus, covalent functionalization might be appropriate for mechanical improvement in low-strength materials. However, non-covalent functionalization is suitable for electrical enhancement in low-conducting nanomaterials.     

Investigating the effect of interphase and surrounding resin on carbon nanotube free vibration behavior

The free vibration analysis of a carbon nanotube (CNT) embedded in a volume element is performed using 3D finite element (FE) and analytical models. Three approaches consist of molecular and continuum mechanics FE methods and continuum analytical method are employed to simulate the CNT, interphase region and surrounding matrix. The bonding between CNT and polymer is treated as non-perfect bonding using van der Waals and triple phase material interaction in first and second approaches. In analytical approach a perfect bonding is assumed between nanotube and matrix. First, natural frequencies of CNT under different boundary conditions and aspect ratios are obtained by three approaches and the results are compared with published data. The results show the frequency response variations of CNT in GHz to THz range. Subsequently, vibration behaviors of CNT/polymer are evaluated and the results revealed the importance of interphase region role in the performance of nanocomposites. The results also showed the convergence of the natural frequencies for 1–2.5% of CNT volume in high aspect ratios using three methods, so that the interphase effects is negligible. In addition, it is observed that the molecular method due to interphase role has proper performance in vibration behavior investigation of volume elements.     

Focused-electron-beam-induced processing (FEBIP) for emerging applications in carbon nanoelectronics

Focused-electron-beam-induced processing (FEBIP), a resist-free additive nanomanufacturing technique, is an actively researched method for “direct-write” processing of a wide range of structural and functional nanomaterials, with high degree of spatial and time-domain control. This article attempts to critically assess the FEBIP capabilities and unique value proposition in the context of processing of electronics materials, with a particular emphasis on emerging carbon (i.e., based on graphene and carbon nanotubes) devices and interconnect structures. One of the major hurdles in advancing the carbon-based electronic materials and device fabrication is a disjoint nature of various processing steps involved in making a functional device from the precursor graphene/CNT materials. Not only this multi-step sequence severely limits the throughput and increases the cost, but also dramatically reduces the processing reproducibility and negatively impacts the quality because of possible between-the-step contamination, especially for impurity-susceptible materials such as graphene. The FEBIP provides a unique opportunity to address many challenges of carbon nanoelectronics, especially when it is employed as part of an integrated processing environment based on multiple “beams” of energetic particles, including electrons, photons, and molecules. This avenue is promising from the applications’ prospective, as such a multi-functional (electron/photon/molecule beam) enables one to define shapes (patterning), form structures (deposition/etching), and modify (cleaning/doping/annealing) properties with locally resolved control on nanoscale using the same tool without ever changing the processing environment. It thus will have a direct positive impact on enhancing functionality, improving quality and reducing fabrication costs for electronic devices, based on both conventional CMOS and emerging carbon (CNT/graphene) materials.     

Carbon Nanotube Reinforced Titanium Metal Matrix Composites Prepared by Powder Metallurgy—A Review

Titanium-based metal composites (TMCs) are showing great potential to replace existing traditional materials in aerospace, automotive, and other high temperature engineering applications. This is due to their excellent mechanical, thermal, and physical properties and improved strength to weight ratio. Weight savings in the aerospace industry results in higher efficiency. Carbon nanotubes (CNTs), because of their low density and high Young's modulus, are considered to be an excellent reinforcement for metal matrix composites (MMCs). In the last 20 years extensive research has been carried out to investigate the combination of carbon nanotubes with aluminum, nickel, copper, magnesium, and other metal matrices. The production techniques such as mechanical alloying through powder metallurgy routes and their effects on the mechanical properties of CNT reinforced TMCs are reviewed in this article. The role of the volume fraction of carbon nanotubes and their dispersion into the metal matrix are highlighted. Governing equations to predict the mechanical and tribological properties of CNT reinforced titanium matrix composites are deduced. With the help of this initial prediction of properties, the optimal processing parameters can be optimized. Successful development of CNT reinforced TMCs would result in better wear and mechanical behavior and enhance their ability to withstand high temperature and structural loading environments.     

Influence of covalent and non-covalent modification of graphene on the mechanical,thermal and electrical properties of epoxy/graphene nanocomposites: a review

Abstract

Graphene is emerged as a highly sought after reinforcing filler for epoxy matrix in view of its superior electrical, mechanical and thermal properties. Dispersion of low concentration of graphene can significantly enhance the epoxy/graphene nanocomposites properties. Dispersion of graphene in epoxy matrix depends on processing protocols used, and interfacial interaction between epoxy matrix and graphene. Interfacial interaction between epoxy matrix and graphene can be achieved by covalent and non-covalent modification of graphene. This paper comprehensively review the influence of different processing protocols adopted for the processing of epoxy/graphene nanocomposites, and its effect on mechanical, thermal and electrical properties. In addition, covalent and non-covalent strategies adopted for modification of graphene, and its influence on mechanical, thermal and electrical properties of epoxy/graphene nanocomposites are extensively discussed. The future challenges associated with graphene reinforced epoxy nanocomposites processing have been discussed.     

Micromechanical properties of poly(butylene terephthalate) nanocomposites with single- and multi-walled carbon nanotubes

Polymer nanocomposites with carbon nanotubes (CNT) are becoming important structural materials because of their superior mechanical properties and easy processability. The objective of the work is to investigate the influence of small amounts of single walled carbon nanotubes (SWCNT), as well as multi-walled carbon nanotubes (MWCNT), on the microhardness of a thermoplastic polymer such as poly(butylene terephthalate) (PBT). The nanocomposites were obtained by introducing the CNT into the reaction mixture during the synthesis of PBT. The polymers without carbon nanotubes (reference material) and with carbon nanotubes were synthesized using an in-situ polycondensation reaction process. Weight percentages ranging from 0.01 to 0.2 wt% of the single walled and from 0.01 to 0.35 wt% of the multi-walled nanotubes were dispersed in 1,4-butanediol (BD) by ultrasonication and by ultra high speed stirring. The nanocomposites were extruded followed by injection molding. The samples were characterized by electron microscopy and microindentation hardness techniques. The variations of the micromechanical properties (indentation hardness) of the nanocomposites with nanotube content and with temperature are discussed in the light of the stress transfer between the polymer matrix and nanotubes, the degree of dispersion, the nature of the tubes and other structural parameters.     

Improvement of Mechanical Properties and Ultraviolet Resistance of Polyethylene Pipe Materials Using High Density Polyethylene Matrix Grafted Carbon Black

In recent years, high grade high density polyethylene (HDPE) pipe materials are being more and more widely used for water and gas supply. Carbon black (CB) is usually used as an anti-UV-light reagent for pipe materials. However, homogeneous dispersion of CB in the HDPE matrix and modification of the interface has always been a great challenge. In this work, HDPE matrix grafted CB (HDPE-g-CB) was successfully prepared through HDPE radicals formation by a thermo-mechanical method and subsequent radical capture by the CB surface. The weight percentage of grafted HDPE approached 10 wt% and the modification sharply reduced the surface free energy of the CB. The SEM (scanning electron micrographs) and TEM (transmission electron microscopy) results showed that HDPE-g-CB was uniformly dispersed in the HDPE pipe materials and the domain size of the dispersed phase was remarkably decreased from that in HDPE/CB. Therefore, compared with the HDPE/CB, the mechanical properties and ultraviolet (UV) resistance of HDPE/HDPE-g-CB were significantly improved, positively influencing the expected life span of pipelines.     

Mechanical Properties of Ni-Coated Single Graphene Sheet and Their Embedded Aluminum Matrix Composites

The effects of Ni coating on the mechanical behaviors of single graphene sheet and their embedded Al matrix composites under axial tensionare investigated using molecular dynamics (MD) simulation method. Theresults show that the Young's moduli and tensile strength of grapheneobviously decrease after Ni coating. The results also show that the mechanical properties of Al matrix can be obviously increased by embedding asingle graphene sheet. From the simulation, we also find that the Young'smodulus and tensile strength of the Ni-coated graphene/Al composite isobviously larger than those of the uncoated graphene/Al composite. Theincreased magnitude of the Young's modulus and tensile strength ofgraphene/Al composite are 52.27 and 32.32 at 0.01 K, respectively,due to Ni coating. By exploring the effects of temperature on the mechanicalproperties of single graphene sheet and their embedded Al matrix composites, it is found that the higher temperature leads to the lower critical strain and tensile strength.     

Carbon Black–Filled Styrene Butadiene Rubber Masterbatch Based on Simple Mixing of Latex and Carbon Black Suspension: Preparation and Mechanical Properties

An improved process was developed for the production of carbon black (CB)–filled styrene butadiene rubber masterbatch (SBR-CB-MB) using a simple latex/CB mixing technology; the improvement comprised processing the CB as an emulsifier-free aqueous suspension by high-rate shearing. Tensile and tear strength, dynamic compression behaviors, the Payne effect, equilibrium swelling and bound rubber of the SBR-CB-MB and dry mixing CB filled SBR (SBR-CB-DM), covering a wide range of CB loading (45–70 phr), were investigated and compared. It was found that the tensile and tear strength, heat buildup and compression set, abrasion volume loss, and the Payne effect of the SBR-CB-MB were lower than those of the SBR-CB-DM, while the bound rubber content were higher, indicating good CB/rubber interaction in the SBR-CB-MB. SEM analysis showed that no free CB could be found on the surface or inside of the granular SBR-CB-MB particles, indicating good CB dispersion in the rubber matrix.     

The effective stiffness of an embedded graphene in a polymeric matrix

Modeling the real sizes of an embedded graphene and the surrounding polymer of a representative volume element in a molecular dynamics simulation is a tedious task. The less computational limitations made the continuum-based method a good candidate for modeling of nanocomposites. However, having a good knowledge of mechanical properties of the embedded graphene in a polymeric matrix is a challenge for employing a continuum-based method. Since the applied stress on the graphene/epoxy nanocomposites has not been directly transferred to the embedded graphene, it brings the following question to mind. Is the stiffness of the embedded graphene different from that of the isolated one? To answer to this question, a model was developed by combining the molecular dynamic simulation and the finite element method to calculate the stiffness of an embedded graphene in a polymeric matrix. The results show that the longitudinal stiffness of the embedded graphene is different from that of the isolated graphene and is a function of its length. The use of this relationship in the micromechanical method leads to consider the nanosize effect in macroscale. The results were compared with some available experimental data to validate the model.     

碳纳米管与石墨烯协同提高导热硅脂热性能

以甲基硅油为基础油,碳纳米管、石墨烯或碳纳米管/石墨烯混杂物为导热填料,制备复合导热硅脂.研究结果表明:以碳纳米管为单一导热填料,碳纳米管管径越小,管长越长,越有利于导热硅脂的导热性能提升。当总填充量在6%、碳纳米管和石墨烯配比为2:1时,导热硅脂的热导率提高19%。碳纳米管对石墨烯纳米片起到了分隔和桥连的作用,提高了石墨烯纳米片的分散性,有利于三维热传导网络的形成,进而提高导热硅脂的热传导性能。     

Graphene oxides and carbon nanotubes embedded in polyacrylonitrile-based carbon nanofibers used as electrodes for supercapacitor

This study investigates the use of graphene oxides (GOs) and carbon nanotubes (CNTs) embedded in polyacrylonitrile-based carbon nanofibers (GO–CNT/CNF) as electrodes for the supercapacitor. GO–CNT/CNF was prepared by electrospinning, and was subsequently stabilized and activated. The specific capacitance of GO–CNT/CNF is 120.5 F g⁻¹ in 0.5 M Na₂SO₄ electrolyte, which is higher than or comparable to the specific capacitances of carbon-based materials in neutral aqueous electrolyte, as prepared in this study. GO–CNT/CNF also exhibits a superior cycling stability, and 109% of the initial specific capacitance after 5000 cycles. The high capacitance of GO–CNT/CNF could be attributed to the edge planes and the functional groups of GO, the highly electrical conductivity of CNT, and the network structure of the electrode.     

Processing and properties of carbon nanofibers reinforced epoxy powder composites

Commercially available CNFs (diameter 30–300 nm) have been used to develop both bulk and coating epoxy nanocomposites by using a solvent-free epoxy matrix powder. Processing of both types of materials has been carried out by a double-step process consisting in an initial physical premix of all components followed by three consecutive extrusions. The extruded pellets were grinded into powder and sieved. Carbon nanofibers powder coatings were obtained by electrostatic painting of the extruded powder followed by a curing process based in a thermal treatment at 200 °C for 25 min. On the other hand, for obtaining bulk carbon nanofibers epoxy composites, a thermal curing process involving several steps was needed. Gloss and mechanical properties of both nanocomposite coatings and bulk nanocomposites were improved as a result of the processing process. FE-SEM fracture surface microphotographs corroborate these results. It has been assessed the key role played by the dispersion of CNFs in the matrix, and the highly important step that is the processing and curing of the nanocomposites. A processing stage consisted in three consecutive extrusions has reached to nanocomposites free of entanglements neither agglomerates. This process leads to nanocomposite coatings of enhanced properties, as it has been evidenced through gloss and mechanical properties. A dispersion limit of 1% has been determined for the studied system in which a given dispersion has been achieved, as the bending mechanical properties have been increased around 25% compared with the pristine epoxy resin. It has been also demonstrated the importance of the thickness in the nanocomposite, as it involves the curing stage. The complex curing treatment carried out in the case of bulk nanocomposites has reached to reagglomeration of CNFs.     

Release potential of single-wall carbon nanotubes produced by super-growth method during manufacturing and handling

We investigated the release potential of single-wall carbon nanotubes (CNTs) produced by the super-growth method during their manufacturing and handling processes at a research facility. We generally sampled air at points both outside and inside of protective enclosures such as a glove box and fume hood. Sampling the air outside of the enclosures was intended to evaluate the actual exposure of workers to CNTs, while sampling the air inside the enclosures was performed to quantify the release of CNTs to the air in order to estimate the potential exposure of workers without protection. The results revealed that airborne CNTs were generated when (1) CNTs were separated from the substrates using a spatula and placed in a container in a glove box; (2) an air gun was used to clean the air filters (containing dust that included CNTs) of a vacuum cleaner; (3) a vacuum cleaner was used to collect CNTs (emission with exhaust air from the cleaner); (4) the container of CNTs was opened; and (5) CNTs in the bin of the cleaner were transferred to a container. In these processes, airborne CNTs were only found inside the enclosures, except for a small amount of CNTs released from the glove box when it was opened. Electron microscopic observations of aerosol particles found CNT clusters, which were fragments of CNT forests, with sizes ranging from submicrometers to tens of micrometers.