Carbon nanotubes/TiO2 nanotubes composite photocatalysts for efficient degradation of methyl orange dye

A series of carbon nanotubes/TiO2 nanotubes （CNTs/TNTs） composite photocatalysts were successfully prepared by incorporation of CNTs in HNO3 washing process. These photocatalysts were characterized by XRD, N2 physical adsorption, UV-vis diffuse reflectance spectroscopy, TEM and Raman spectroscopy, respectively, and their photocatalytic activities were tested by using methyl orange （MO） as a model compound. Also, the effects of amount of CNTs incorporated, calcination temperature and amount of catalyst on the photocatalytic activity of the composite photocatalyst were systematically investigated. The results show that the CNTs/TNTs composite exhibits much higher photocatalytic activity than that of the TNTs or CNTs alone.     

In situ synthesis of CNTs/Fe–Ni/TiO2 nanocomposite by fluidized bed chemical vapor deposition and the synergistic effect in photocatalysis

Carbon nanotube (CNTs)/Fe–Ni/TiO₂ nanocomposite photocatalysts have been synthesized by an in situ fluidized bed chemical vapor deposition (FBCVD) method. The composite photocatalysts were characterized by XRD, Raman spectroscopy, BET, FESEM, TEM, UV–vis spectroscopy, and XPS. The results showed that the CNTs were grown in situ on the surface of TiO₂. Fe(III) in TiO₂ showed no chemical changes in the growth of CNTs. Ni(II) was partly reduced to metal Ni in the FBCVD process, and the metal Ni acted as a catalyst for the growth of CNTs. The photocatalytic activities of CNTs/Fe–Ni/TiO₂ decreased with the rise of the FBCVD reaction temperature. For the sample synthesized at low FBCVD temperature (500 °C), more than 90% and nearly 50% of methylene blue were removed under UV irradiation in 180 min and under visible light irradiation in 300 min, respectively. The probable mechanism of synergistic enhancement of photocatalysis on the CNTs/Fe–Ni/TiO₂ nanocomposite is proposed.     

Mechanical behaviour of carbon nanotubes under combined twisting–bending

The main objective of this paper is to investigate the mechanical behaviour (strength and stiffness) of carbon nanotubes (CNTs) under combinations of bending and twisting. In order to achieve this goal, molecular dynamics (MD) simulations of bended and twisted CNTs are performed. The LAMMPS code is used, the AIREBO potential is considered for CC bonds, the temperature is kept at 300 K and incremental bending and twisting rotations are imposed to the CNT. Two types of CNTs are analyzed, including zig-zag (8,0) and armchair (5,5) CNTs with similar radius and length. The CNTs are also analyzed for pure bending and pure twisting. The main results are shown in the form of diagrams of energy and moment against imposed rotations. Some relevant conclusions are drawn concerning the influence of loading (bending and twisting) on the stiffness, strength and failure of CNTs: namely, it is concluded that armchair CNTs possess higher strength and fracture toughness under twisting–bending loading than zigzag CNTs; additionally, it is found that both CNTs (armchair and zigzag) still support moderate-to-high bending levels without failure after being extremely twisted and torsionally buckled, even for twisting angles four times those corresponding to torsional buckling; finally, the results prove that CNTs, mostly armchair ones, exhibit very high twisting–bending stiffness and strength and can be used with confidence as torsional spring elements in nanoelectromechanical systems (NEMS).     

A theory of plasticity for carbon nanotube reinforced composites

Carbon nanotubes (CNTs) possess exceptional mechanical properties, and when introduced into a metal matrix, it could significantly improve the elastic stiffness and plastic strength of the nanocomposite. But current processing techniques often lead to an agglomerated state for the CNTs, and the pristine CNT surface may not be able to fully transfer the load at the interface. These two conditions could have a significant impact on its strengthening capability. In this article we develop a two-scale micromechanical model to analyze the effect of CNT agglomeration and interface condition on the plastic strength of CNT/metal composites. The large scale involves the CNT-free matrix and the clustered CNT/matrix inclusions, and the small scale addresses the property of these clustered inclusions, each containing the randomly oriented, transversely isotropic CNTs and the matrix. In this development the concept of secant moduli and a field fluctuation technique have been adopted. The outcome is an explicit set of formulae that allows one to calculate the overall stress-strain relations of the CNT nanocomposite. It is shown that CNTs are indeed a very effective strengthening agent, but CNT agglomeration and imperfect interface condition can seriously reduce the effective stiffness and elastoplastic strength. The developed theory has also been applied to examine the size (diameter) effect of CNTs on the elastic and elastoplastic response of the composites, and it was found that, with a perfect interface contact, decreasing the CNT radius would enhance the overall stiffness and plastic strength, but with an imperfect interface the size effect is reversed. A comparison of the theory with some experiments on the CNT/Cu nanocomposite serves to verify the applicability of the theory, and it also points to the urgent need of eliminating all CNT agglomeration and improving the interface condition if the full potential of CNT reinforcement is to be realized.     

Two-fold enhancement in tensile strength of carbon nanotube–carbon fiber hybrid epoxy composites through combination of electrophoretic deposition and alternating electric field

A new carbon nanotube (CNT)–hybridized carbon fiber (CF) was introduced in an attempt to improve interfacial strength between CF and polymeric matrix. Amine-functionalized CNTs was radially deposited on the CF surface through a combination of alternating electric field with electrophoretic deposition process. Radial deposition of CNTs on CF formed a unique porous structure around CF that could significantly increase the interfacial adhesion through interlocking of polymeric matrix. Tensile properties and fatigue life of the reinforced composites were investigated in order to study the effect of interfacial adhesion on mechanical properties of reinforced composites. Results indicate that the radial deposition of CNT on CF can remarkably enhance the compatibility of polymeric matrix with CF. This improvement in compatibility of polymeric matrix with CNT–hybridized CF resulted in considerable enhancement in mechanical properties of composites. The interfacial reinforcing mechanism was explored through fractography of reinforced composites and possible failure modes have been precisely discussed.     

Rheological characterization of carbon nanotubes/poly(ethylene oxide) composites

Rheological properties of poly(ethylene oxide) nanocomposites embedded with carbon nanotubes (CNTs) were investigated in the present study. It was found that the CNT nanocomposites had a higher effective filler volume fraction than the real filler volume fraction, which yielded a drastic enhancement of shear viscosity. As the CNT loading in the nancomposites increases, non-Newtonian behavior was observed at the low-shear-rate region in the steady shear experiments. Oscillatory dynamic shear experiments showed that more addition of the CNTs led to stronger solidlike and nonterminal behaviors. To identify a dispersion state of the CNTs, field emission scanning electron spectroscopy and transmission electron microscopy were adopted and thermal analysis was also performed by using differential scanning calorimetry. The existence of percolated network structures of the CNTs even at a low CNT loading was verified by rheological properties and electrical conductivities.     

Catalytic ability of MgO to break CH bonds during slurry oil carbon deposition

Although MgO has been widely used for the MgO-templated synthesis of carbon materials, little attention has been paid to MgO’s catalytic function during carbon deposition. Here, a systematic analysis of the products of slurry oil (SO) carbonization with and without MgO templates present indicates that MgO catalytically promoted the breakage of CH bonds by immobilizing heavy oil molecules on MgO surfaces and the attractive interaction between hydrogen and MgO. Compared with the carbonization of SO alone, a notably higher H₂ concentration and a lower hydrocarbon concentration was observed in the tail gas, a higher solid yield and a lower degree of graphitization of the carbon product were observed when MgO was also present. Furthermore, treatment at 900 °C in the presence of MgO efficiently enhanced the capacitance and rate capability of the as-obtained porous carbon when tested as an electrode material for supercapacitors. These results suggest that the catalytic function of MgO could exist in all MgO-templated syntheses and in the heat treatment of porous carbons and graphene.     

The influence of mechanical deformation on the electrical properties of single wall carbon nanotubes

Recent experimental studies and atomistic simulations have shown that carbon nanotubes (CNTs) display strong interplay between the mechanical deformation and electrical properties. We have developed a simple and accurate method to determine atom positions in a uniformly deformed CNT via a continuum analysis based on the interatomic potential. A shift vector is introduced to ensure the equilibrium of atoms. Such an approach, involving only three variables for the entire CNT, agrees very well with the molecular mechanics calculations. We then study the effect of mechanical deformation on the band gap change of single wall CNTs under tension, torsion, and combined tension/torsion via the k-space tight-binding method. Prior studies without this shift vector lead to significant overestimation of the band gap change. It is established that the conducting CNTs may easily become semi-conducting ones subject to mechanical deformation, but the semi-conducting CNTs never become conducting ones upon deformation.     

Nucleate boiling heat transfer in aqueous solutions with carbon nanotubes up to critical heat fluxes

In this study, pool boiling heat transfer coefficients (HTCs) and critical heat fluxes (CHFs) are measured on a smooth square flat copper heater in a pool of pure water with and without carbon nanotubes (CNTs) dispersed at 60 °C. Tested aqueous nanofluids are prepared using multi-walled CNTs whose volume concentrations are 0.0001%, 0.001%, 0.01%, and 0.05%. For the dispersion of CNTs, polyvinyl pyrrolidone polymer is used in distilled water. Pool boiling HTCs are taken from 10 kW/m² to critical heat flux for all tested fluids. Test results show that the pool boiling HTCs of the aqueous solutions with CNTs are lower than those of pure water in the entire nucleate boiling regime. On the other hand, critical heat flux of the aqueous solution is enhanced greatly showing up to 200% increase at the CNT concentration of 0.001% as compared to that of pure water. This is related to the change in surface characteristics by the deposition of CNTs. This deposition makes a thin CNT layer on the surface and the active nucleation sites of the surface are decreased due to this layer. The thin CNT layer acts as the thermal resistance and also decreases the bubble generation rate resulting in a decrease in pool boiling HTCs. The same layer, however, decreases the contact angle on the test surface and extends the nucleate boiling regime to very high heat fluxes and reduces the formation of large vapor canopy at near CHF. Thus, a significant increase in CHF results in.     

An atomistic-based continuum theory for carbon nanotubes: analysis of fracture nucleation

Carbon nanotubes (CNTs) display unique properties and have many potential applications. Prior theoretical studies on CNTs are based on atomistic models such as empirical potential molecular dynamics (MD), tight-binding methods, or first-principles calculations. Here we develop an atomistic-based continuum theory for CNTs. The interatomic potential is directly incorporated into the continuum analysis through constitutive models. Such an approach involves no additional parameter fitting beyond those introduced in the interatomic potential. The atomistic-based continuum theory is then applied to study fracture nucleation in CNTs by modelling it as a bifurcation problem. The results agree well with the MD simulations.     

碳纳米管应变传感器的性能分析：实验偏振模式的影响机制

碳纳米管作为一种拉曼力学传感介质具有优异的力学性质及共振、偏振拉曼特性。将碳纳米管散布在基体材料中,即可实现局部应力/应变的测量。受到光学衍射极限的限制,常规的远场拉曼光谱得到的是一定区域内众多碳管的平均散射信息。本文综合考虑了采样点内各方向碳管的影响,并对碳管散射的共振状态、碳管的分布状态、拉曼系统的偏振构型及偏振方向等实验因素对碳纳米管应变传感器性能的影响进行了深入分析,采用分峰和重构的方法定量地给出了不同实验模式下采样点内的拉曼信息组成以及各种实验模式的测量精度。分析和对比表明,采用双偏振构型且偏振方向沿荷载施加方向时的测量精度最高,即最优的实验模式。     

Mechanics of hydrogen storage in carbon nanotubes

A continuum mechanics model is established for hydrogen storage in single- and multi-wall carbon nanotubes (CNTs) and the bundle of single-wall CNTs. The model accounts for the deformation of CNTs, and van der Waals interactions among hydrogen molecules and between hydrogen and carbon atoms. The analytical expressions of hydrogen storage (number of hydrogen molecules per unit volume) in CNTs are obtained, and are validated by atomistic simulations. CNTs are categorized as tiny, small, medium and large CNTs; tiny CNTs cannot achieve the goals of hydrogen storage (62 kg/m³ and 6.5 wt% of hydrogen set by the US Department of Energy) without fracture; small CNTs are strained during hydrogen storage; medium CNTs can achieve the above goals without the strain and do not self collapse; and large CNTs may self collapse upon the release of hydrogen.     

Multiscale computations for carbon nanotubes based on a hybrid QM/QC (quantum mechanical and quasicontinuum) approach

An effective multiscale computing scheme based on QM/QC (quantum mechanics/quasicontinuum) is applied for simulation of Carbon nanotubes (CNTS) mechanics. First, quasicontinuum simulation of deformations of curved crystalline structures is conducted to examine the fully nonlocal behavior of CNTs with the aid of high-order interpolation functions and the “cluster” concept, which facilitates accurate energy approximation for crystals. Next, a multiscale computing approach based on QM/QC hybridization is devised, and applied for simulation of CNT mechanics. The bonding configuration changes, e.g. bond breaking or creation, near defect sites are correctly represented with the QM/QC hybrid model. For studying electronic properties coupled with the mechanical deformation of CNTs, the change of the electrical properties from an initial semiconductor into metal under mechanical bending is investigated. Single-walled CNTs having various types of defects and subjected to uniaxial tension are considered for fracture. The theoretical strength of the CNTs in the presence of each defect is computed based on the QM/QC hybrid scheme, wherein the defect neighborhood is modeled as a QM zone for a first-principle-based calculation using density functional theory (DFT), and the remaining area as a QC zone. This multiscale computing approach greatly improves the accuracy in the prediction of the failure strains of CNTs over a purely molecular mechanical or quasicontinuum method.     

Dispersion of multi-walled carbon nanotubes in PDMS/PB blend

In this study, the sequential dispersion of multi-walled carbon nanotubes (CNTs) in PDMS/PB (polydimethylsiloxane/polybutene) blends and the change of blend morphology by the dispersion of CNTs were investigated by rheological and morphological observations. The dispersion of CNTs into PDMS/PB blend was accomplished by the dilution of the CNT master (2?wt.% CNT in PDMS) in PDMS/PB blend using an extensional mixer. The morphological study shows that under the extensional flow, CNTs in the dispersed CNT master phase are mainly broken up by tip-streaming and the continuous pinching-off of PDMS drops during morphology evolution enhances the dispersion of CNT. It has been shown that CNTs can be disentangled as in the case of dispersing CNTs in a Boger fluid. Rheological data and TEM observations show that it is not simply a mixing of two phases and the CNTs in the master phase can be dispersed in the single CNT level.     

Non-local effects on the non-linear modes of vibration of carbon nanotubes under electrostatic actuation

Carbon nanotubes (CNTs) based NEMS with electrostatic sensing/actuation may be employed as sensors, in situations where it is fundamental to understand their dynamic behaviour. Due to displacements that are large in comparison with the thickness and to the non-linearity of the electrostatic force, these CNT based NEMS operate in the non-linear regime. The knowledge of the modes of vibration of a CNT provides a picture of what one may expect from its dynamic behaviour not only in free, but also in forced vibrations. In this paper, the non-linear modes of vibration of CNTs actuated by electrostatic forces are investigated. For that purpose, a p-version finite element type formulation is implemented, leading to ordinary differential equations of motion in the time domain. The formulation takes into account non-local effects, which influence the inertia and the stiffness of CNTs, as well as the electrostatic actuation. The ordinary differential equations of motion are transformed into algebraic equations of motion via the harmonic balance method (HBM) and then solved by an arc-length continuation method. Several harmonics are considered in the HBM. The importance of non-local effects, combined with the geometrical non-linearity and with the action of the electrostatic force, is analysed. It is found that different combinations of these effects can result in alterations of the natural frequencies, variations in the degrees of softening or hardening, changes in the frequency content of the free vibrations, and alterations in the mode shapes of vibration. It is furthermore found that the small scale, here represented by the non-local theory, has an effect on interactions between the first and higher order modes which are induced by the geometrical and material non-linearities of the system.     

CARBON NANOTUBES VIA METHANE DECOMPOSITION ON AN ALUMINA SUPPORTED COBALT AEROGEL CATALYST

An alumina-supported cobalt aerogel catalyst prepared from a sol-gel and a supercritical drying method was used in the catalytic decomposition of methane.The physical-chemical properties of the catalyst were characterized and its activity for methane decomposition was investigated.The effects of calcination and reaction temperatures on the activity of the catalyst and the morphology of the carbon nanotubes produced were discussed.A COAl2O4 spinel structure formed in the calcined catalyst.The quantity of the nanotubes produced in the reaction increases with the amount of cobalt in the reduced catalyst.A higher reaction temperature leads to a higher reaction rate,though faster deactivation of the catalyst occurs with the change.The carbon nanotubes grown on the catalyst have smooth walls and uniform diameter distribution.     

Multi-walled carbon nanotubes added to Na2CO3/MgO composites for thermal energy storage

Na2CO3/MgO composites with added multi-walled carbon nanotubes （MWCNTs） were prepared and tested as phase change materials （PCMs） for thermal energy storage. Na2CO3/MgO composite PCMs were prepared and their chemical compatibility and thermal stability were studied. MWCNTs introduced with Na2CO3/MgO composite PCMs were also investigated and scanning electron microscopy （SEM） characterization was used to demonstrate the uniform dispersion of MWCNTs in Na2CO3/MgO composite PCMs. The composites with added MWCNTs still display good thermal stability with mass losses lower than 5%. Introducing MWCNTs into composite Na2CO3/MgO PCMs by material formation/calcination signifi.cantly enhances the thermal conductivity of the composite PCMs. The thermal conductivity of the composite PCMs was found to increase with an increase in the weight fraction of the added MWCNTs and an increase in the testing temperature. This study may present a promising way to prepare high temperature phase change materials with superior properties such as improved thermal stability.     

A semi-analytical approach for calculating the equilibrium structure and radial breathing mode frequency of single-walled carbon nanotubes

A semi-analytical model for determining the equi-librium configuration and the radial breathing mode (RBM) frequency of single-wall carbon nanotubes (CNTs) is pre-sented. By taking advantage of the symmetry characteristics, a CNT structure is represented by five independent vari-ables. A line search optimization procedure is employed to determine the equilibrium values of these variables by minimizing the potential energy. With the equilibrium con-figuration obtained, the semi-analytical model enables an efficient calculation of the RBM frequency of the CNTs. The radius and radial breathing mode frequency results obtained from the semi-analytical approach are compared with those from molecular dynamics (MD) and ab initio calculations. The results demonstrate that the semi-analytical approach offers an efficient and accurate way to determine the equilib-rium structure and radial breathing mode frequency of CNTs.     

Carbon nanotubes coated with platinum nanoparticles as anode of biofuel cell

A hybrid system of carbon nanotubes (CNTs) coated with poly (amidoamine) (PAMAM) dendrimer-encapsulated platinum nanoparticles (Pt-DENs) and glucose oxidase (GOx) was prepared through the layer-by-layer (LbL) self-assembly approach and then used as anode in enzyme-based biofuel cells (BFCs). The assembly process was monitored by ζ-potential measurement, and the as-resulted Pt-DENs/CNTs nanocomposites were characterized by transmission electron microscopy (TEM). The performance of electrodes modified by Pt-DENs/CNTs was also investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). We found that the Pt-DENs/CNTs could enhance the electron transfer between the redox centers in enzyme and the electrode surfaces. Furthermore, by employing the Pt-DENs/CNTs modified electrodes as anode, the enzyme-based BFCs operated in a solution containing glucose generated an open-circuit voltage of approximately 640.0 mV and a maximum current density of about 90.0 μA/cm², suggesting that Pt-DENs/CNTs may serve as an alternative anode to previously used noble metals in BFC applications.     

CFD modeling of catalyst pellet for oxidative coupling of methane: Heat transfer and reaction

This study deals with the phenomena occuring at single-pellet catalyst scale for the oxidative coupling of methane where heat transfer plays an important role. Computational fluid dynamics (CFD) is used for obtaining detailed rate and temperature profiles through the porous catalytic pellet where reaction and diffusion compete. Intra-particle temperature and concentration gradients were taken into account by solving heat transfer coupled with continuity equations in the catalyst pellet. In heat transfer, the energy term due to highly exothermic reaction was considered. Two external programs were successfully implemented into the CFD-code as kinetic and heat of reaction terms. Simulation results showed that reaction was favored at the beginning for the pellet, followed by diffusion predomination. The results of CFD simulation indicate that temperature variation within the catalyst pellet is <2 K due to exothermic oxidation. The results showed further that exothermic oxidation reactions occurred prior to endothermic coupling reaction in the pellet.