A new method for characterizing the interphase regions of carbon nanotube composites

The elastic properties of a carbon nanotube (CNT) reinforced composite are affected by many factors such as the CNT–matrix interphase. As such, mechanical analysis without sufficient consideration of these factors can give rise to incorrect predictions. Using single-walled carbon nanotube (SWCNT) reinforced Polyvinylchloride (PVC) as an example, this paper presents a new technique to characterize interphase regions. The representative volume element (RVE) of the SWCNT–PVC system is modeled as an assemblage of three phases, the equivalent solid fiber (ESF) mimicking the SWCNT under the van der Waals (vdW) forces, the dense interphase PVC of appropriate thickness and density, and the bulk PVC matrix. Two methods are proposed to extract the elastic properties of the ESF from the atomistic RVE and the CNT-cluster. Using atomistic simulations, the thickness and the average density of interphase matrix are determined and the elastic properties of amorphous interphase matrix are characterized as a function of density. The method is examined in a continuum-based three-phase model developed with the aid of molecular mechanics (MM) and the finite element (FE) method. The predictions of the continuum-based model show a good agreement with the atomistic results verifies that the interphase properties of amorphous matrix in CNT-composites could be approximated as a function of density. The results show that ignoring either the vdW interaction region or the interphase matrix layer can bring about misleading results, and that the effect of internal walls of multi-walled carbon nanotubes (MWCNTs) on the density and thickness of the dense interphase is negligible.     

Effect of CNT length and CNT-matrix interphase in carbon nanotube (CNT) reinforced composites

The load transfer mechanisms and effective moduli of single-walled nanotube (SWNT) reinforced composites are studied using a continuum model. A “critical” fiber length is defined for full load transfer by numerically evaluating the strain-energy-changes for different fiber lengths. The effective longitudinal Young’s modulus and bulk modulus of the composite are derived. The effect of the interphase is also discussed. The results indicate the fiber length is critical both to the load transfer efficiency and effective moduli of the composite. The SWNT-matrix interphase plays an important role in load transfer efficiency but affects the effective moduli only slightly.     

Creep and recovery of polypropylene/carbon nanotube composites

The creep and recovery of polypropylene/multi-walled carbon nanotube composites were studied. It was found for thermoplastics in general that the creep strain reduces with decreased temperature, and with enhanced content of carbon nanotubes. The incorporation of nanotubes improved the recovery property remarkably, especially at high temperature. The unrecovered creep strain of nanocomposites with content of 1 and 2.8 vol.% carbon nanotubes decreased by 53% and 73% compared to that of polymer matrix. To understand the mechanisms, the Burger’s model and Weibull distribution function were employed since the variations in the simulating parameters illustrated the influence of nano-fillers on the creep and recovery performance of the bulk matrix. To further study the recovery properties, the particular contribution of each Burger’s element to the total deformation was obtained and the recovery percentage was calculated. The time-temperature-superposition-principle was applied to predict the long-term creep behavior.     

Filament stretching of carbon nanotube suspensions

This paper reports the application of a recently developed filament stretching protocol for the study of the extensional rheology of both treated and untreated carbon nanotubes (CNT) suspended within an epoxy resin. It was experimentally observed that filaments formed by treated and untreated CNT suspensions behaved differently after initial stretching. The filament thinning process of the base epoxy was consistent with a simple Newtonian fluid, whilst the filament of treated CNT suspensions also thinned in a Newtonian way but with an enhanced extensional viscosity. Filaments formed with untreated CNT suspensions behaved in a non-uniform way with local fluctuation in filament diameter, and it was not possible to obtain reliable extensional viscosity data. Irregularity of the untreated CNT filaments was consistent with coupled optical images, where spatial variation in CNT aggregate concentration was observed. In the case of treated CNT suspensions, the enhanced extensional viscosity was modelled in terms of the alignment of CNTs in the stretching direction, and the degree of alignment was subsequently estimated using a simple orientation model.     

Three-dimensional theory of stability of a carbon nanotube in a matrix

The three-dimensional theory of stability of a carbon nanotube (CNT) in a polymer matrix is presented. The results are obtained on the basis of the three-dimensional linearized theory of stability of deformable bodies. Flexural and helical (torsional) buckling modes are considered. It is proved that the helical (torsional) buckling modes occur in a single CNT (the interaction of neighboring CNTs is neglected) and do not occur in nanocomposites (the interaction of neighboring CNTs is taken into account) __________ Translated from Prikladnaya Mekhanika, Vol. 42, No. 1, pp. 23–37, January 2006.     

Stiffness threshold of randomly distributed carbon nanotube networks

For carbon nanotube (CNT) networks, with increasing network density, there may be sudden changes in the properties, such as the sudden change in electrical conductivity at the electrical percolation threshold. In this paper, the change in stiffness of the CNT networks is studied and especially the existence of stiffness threshold is revealed. Two critical network densities are found to divide the stiffness behavior into three stages: zero stiffness, bending dominated and stretching dominated stages. The first critical network density is a criterion to judge whether or not the network is capable of carrying load, defined as the stiffness threshold. The second critical network density is a criterion to measure whether or not most of the CNTs in network are utilized effectively to carry load, defined as bending–stretching transitional threshold. Based on the geometric probability analysis, a theoretical methodology is set up to predict the two thresholds and explain their underlying mechanisms. The stiffness threshold is revealed to be determined by the statical determinacy of CNTs in the network, and can be estimated quantitatively by the stabilization fraction of network, a newly proposed parameter in this paper. The other threshold, bending–stretching transitional threshold, which signs the conversion of dominant deformation mode, is verified to be well evaluated by the proposed defect fraction of network. According to the theoretical analysis as well as the numerical simulation, the average intersection number on each CNT is revealed as the only dominant factor for the electrical percolation and the stiffness thresholds, it is approximately 3.7 for electrical percolation threshold, and 5.2 for the stiffness threshold of 2D networks. For 3D networks, they are 1.4 and 4.4. And it also affects the bending–stretching transitional threshold, together with the CNT aspect ratio. The average intersection number divided by the fourth root of CNT aspect ratio is found to be an invariant at the bending–stretching transitional threshold, which is 6.7 and 6.3 for 2D and 3D networks, respectively. Based on this study, a simple piecewise expression is summarized to describe the relative stiffness of CNT networks, in which the relative stiffness of networks depends on the relative network density as well as the CNT aspect ratio. This formula provides a solid theoretical foundation for the design optimization and property prediction of CNT networks.     

Transition of electrical conductivity in carbon nanotube/silver particle composite buckypapers

The electrical conductivity of carbon nanotube buckypapers can be dramatically increased by incorporation of silver particles contained in a commercial silver paste.Two methods,co-dispersion during the production of buckypaper and surface coating on a preformed buckypaper,were used to prepare composite buckypapers.The two types of composite buckypapers exhibited very different electrical conductivity profiles.The composite buckypapers prepared by the surface coating method showed a distinct step transition in electrical conductivity at 3 vol%silver content,leading to a 15-fold improvement at 6%silver content.The composite buckypapers prepared by the co-dispersion method showed a gradual change in electrical conductivity with increasing silver particle content,resulting in a five-fold improvement at12%silver content.Surface and sectional morphologies of the two types of composite buckypapers were examined and related to their electrical conductivity profiles.     

A single degree of freedom ‘lollipop’ model for carbon nanotube bundle formation

Current carbon nanotube (CNT) synthesis methods include the production of ordered, free-standing vertically aligned arrays, the properties of which are partially governed by interactions between adjacent tubes. Using material parameters determined by atomistic methods, here we represent individual CNTs by a simple single degree of freedom ‘lollipop’ model to investigate the formation, mechanics, and self-organization of CNT bundles driven by weak van der Waals interactions. The computationally efficient simple single degree of freedom model enables us to study arrays consisting of hundreds of thousands of nanotubes. The effects of nanotube parameters such as aspect ratio, bending stiffness, and surface energy, on formation and bundle size, as well as the intentional manipulation of bundle pattern formation, are investigated. We report studies with both single wall carbon nanotubes (SWCNTs) and double wall carbon nanotubes (DWCNTs) with varying aspect ratios (that is, varying height). We calculate the local density distributions of the nanotube bundles and show that there exists a maximum attainable bundle density regardless of an increase in surface energy for nanotubes with given spacing and stiffness. In addition to applications to CNTs, our model can also be applied to other types of nanotube arrays (e.g. protein nanotubes, polymer nanofilaments).     

Deformation and orientation during shear and elongation of a polycarbonate/carbon nanotubes composite in the melt

In this study, we focused on the elongational rheology and the morphology of an electrically conductive polycarbonate/multiwalled carbon nanotubes (2 wt%) composite in the melt. In shear and melt elongation, the influence of the carbon nanotubes was large when the externally applied stress was small. Consequently, the elastic interactions resulting from the carbon nanotubes dominated in the low frequency range of the shear oscillations. The elongational viscosity of the composite was only moderately influenced by the addition of 2 wt% carbon nanotubes. Transmission electron microscopy investigations of the stretched composite showed that isolated carbon nanotubes were oriented in elongation. In recovery after melt elongation, the recovered stretch of the composite was much smaller than the recovered stretch of pure polycarbonate. This effect is caused by the carbon nanotubes network, which prohibited large extensions of the macromolecules and led to a yield stress of the composite.     

Modulational instability of gap solitons in single-walled carbon nanotube lattices

Modulational instability and nonlinear localized excitations are addressed, in the framework of a one-dimensional diatomic carbon nanotube (CNT) model, using the quasi-discrete approximation. Gap soliton solutions, based on the modulational instability criterion, are studied, where one considers the solutions arising in the upper and lower optical frequency cutoff regimes, and in the upper acoustic frequency cutoff mode. Solutions are found as breathers and double breathers, and their response to interatomic interaction parameters is discussed. Vibrations of the CNTs from the two modes are compared based on their capability of carrying the amount of energy required for specific purposes, either in Microelectronics or in Nano-devices.     

Analysis of the entanglements in carbon nanotube fibers using a self-folded nanotube model

Carbon nanotube (CNT) fibers have shown superb mechanical properties, and have high potential to be used as reinforcements in multifunctional composites. CNT entanglements always exist in CNT fibers and play a crucial role in affecting their mechanical properties. In this study, the CNT entanglement is modeled as two connecting self-folded CNTs (SFCNTs). At large aspect ratios, a CNT is energetically favorable to be self-folded due to the van der Waals interactions between different parts of the CNT. The geometrical characteristics of the SFCNTs, such as the critical length for self-folding as well as the critical effective width and length, are investigated by using both an exact theoretical model and an approximate theoretical model. The tensile properties of the SFCNTs have been examined by using both the approximate theoretical model and atomistic simulations. Good agreements are achieved in the results of these two approaches.     

A cohesive law for carbon nanotube/polymer interfaces based on the van der Waals force

We have established the cohesive law for interfaces between a carbon nanotube (CNT) and polymer that are not well bonded and are characterized by the van der Waals force. The tensile cohesive strength and cohesive energy are given in terms of the area density of carbon nanotube and volume density of polymer, as well as the parameters in the van der Waals force. For a CNT in an infinite polymer, the shear cohesive stress vanishes, and the tensile cohesive stress depends only on the opening displacement. For a CNT in a finite polymer matrix, the tensile cohesive stress remains the same, but the shear cohesive stress depends on both opening and sliding displacements, i.e., the tension/shear coupling. The simple, analytical expressions of the cohesive law are useful to study the interaction between CNT and polymer, such as in CNT-reinforced composites. The effect of polymer surface roughness on the cohesive law is also studied.     

N-doped carbon nanotube encapsulated nZVI as a high-performance bifunctional catalyst for oxidative desulfurization

Great efforts have been made to remove sulfur from fossil fuels to protect the environment. We proposed synthesis of high efficiency oxidation desulfurization (ODS) catalysts by encapsulating nano zero valent iron (nZVI) in self-catalyzed carbon nanotubes. The synthetic strategy features facile hydrothermal and pyrolysis process. The specific surface area, pore structure, and microstructure of the catalysts were characterized by series techniques, and the catalytic ability was evaluated by the reduction of sulfur after oxidation and reflux-extraction. The optimized nZVI@CNT catalyst exhibits outstanding catalytic performance (within 120 min, the oxidative removal rate of DBT reached 96%) and enhanced stability (a 80% retention of initial performance after six cycles.), revealing the effective optimization and modulation between carbon nanotubes and iron particles. This excellent ODS activity originated from the defects of N-doped nanotubes as well as excellent particle dispersion and material transport capacity, which excites highly active free radicals with the assistance of H₂O₂. In addition, the unique two-dimensional tube channel and mesoporous structure promoted the diffusion and transfer of reactants and electrons, leading to high density of active sites. The different experimental conditions confirmed that the material is a bifunctional catalyst integrating adsorption and catalysis. This work provides an creative ideas for the rational design and synthesis of advanced ODS catalysts for fuel oil.     

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.     

The bimodal theory of plasticity: A form-invariant generalisation

The bimodal plasticity model of fibre-reinforced materials is currently available and applicable only in association with thin-walled fibrous composites containing a family of straight fibres which are conveniently assumed parallel with the x₁-axis of an appropriately chosen Cartesian co-ordinate system. Based on reliable experimental evidence, the model suggests that plastic slip in the composite operates in two distinct modes; the so-called matrix dominated mode (MDM) which depends on a matrix yield stress, and the fibre dominated mode (FDM) which depends also on the fibre yield stress. Each mode is activated by different states of applied stress, has its own yield surface (or surfaces) in the stress space and has its own segment on the overall yield surface of the composite. This paper employs theory of tensor representations and produces a form-invariant generalisation of both modes of the model. This generalisation furnishes the model with direct applicability to relevant plasticity problems, regardless of the shape of the fibres or the orientation of the co-ordinate system. It thus provides a proper mathematical foundation that underpins important physical concepts associated with the model while it also elucidates several technical relevant issues. A most interesting of those issues is the revelation that activation of the MDM plastic regime is possible only if the applied stress state allows the fibres to act like they are practically inextensible. Moreover, activation of the more dominant, between the two MDM plastic slip branches is possible only if conditions of material incompressibility hold, in addition to the implied condition of fibre inextensibility. A direct mathematical connection is thus achieved between basic, experimentally verified concepts of the bimodal plasticity model and a relevant mathematical model originated earlier from the theory of ideal fibre-reinforced materials. An additional issue of discussion involves the number of independent yield stress parameters that the bimodal theory needs to take into consideration. Moreover, an analytical expression is provided of a relatively simple mathematical surface that possesses all known features of the FDM yield surface; currently captured with the aid of both experimental and computational means. The present study is guided by the existing relevant experimental evidence which, however, is principally associated with the plastic behaviour of solids reinforced by strong fibres. Nevertheless, several of the outlined developments are expected to be applicable to composite materials containing a single family of more compliant or even weak fibres.     

Multi-scale modeling of tensile behavior of carbon nanotube-reinforced composites

A multi-scale representative volume element (RVE) for modeling the tensile behavior of carbon nanotube-reinforced composites is proposed. The RVE integrates nanomechanics and continuum mechanics, thus bridging the length scales from the nano- through the mesoscale. A progressive fracture model based on the modified Morse interatomic potential is used for simulating the behavior of the isolated carbon nanotubes and the FE method for modeling the matrix and building the RVE. Between the nanotube and the matrix a perfect bonding is assumed until the interfacial shear stress exceeds the corresponding strength. Then, nanotube/matrix debonding is simulated by prohibiting load transfer in the debonded region. Using the RVE, a unidirectional nanotube/polymer composite was modeled and the results were compared with corresponding rule-of-mixtures predictions. A significant enhancement in the stiffness of the polymer owing to the adding of the nanotubes is predicted. The effect of interfacial shear strength on the tensile behavior of the nanocomposite was also studied. Stiffness is found to be unaffected while tensile strength to significantly decrease with decreasing the interfacial shear strength.     

Nonlinear in-plane thermal buckling of rotationally restrained functionally graded carbon nanotube reinforced composite shallow arches under uniform radial loading

The nonlinear in-plane instability of functionally graded carbon nanotube reinforced composite (FG-CNTRC) shallow circular arches with rotational constraints subject to a uniform radial load in a thermal environment is investigated. Assuming arches with thickness-graded material properties, four different distribution patterns of carbon nanotubes (CNTs) are considered. The classical arch theory and Donnell’s shallow shell theory assumptions are used to evaluate the arch displacement field, and the analytical solutions of buckling equilibrium equations and buckling loads are obtained by using the principle of virtual work. The critical geometric parameters are introduced to determine the criteria for buckling mode switching. Parametric studies are carried out to demonstrate the effects of temperature variations, material parameters, geometric parameters, and elastic constraints on the stability of the arch. It is found that increasing the volume fraction of CNTs and distributing CNTs away from the neutral axis significantly enhance the bending stiffness of the arch. In addition, the pretension and initial displacement caused by the temperature field have significant effects on the buckling behavior.     

A simple theory of strain gradient plasticity based on stress-induced anisotropy of defect diffusion

A new strain gradient plasticity theory is formulated to accommodate more than one material length parameter. The theory is an extension of the classical J₂ flow theory of metal plasticity to the micron scale. Distinctive features of the proposed theory as compared to other existing theories are the simplicities of mathematical formulation, numerical implementation and physical interpretation.     

A mathematical basis for strain-gradient plasticity theory. Part II: Tensorial plastic multiplier

A phenomenological, flow theory version of gradient plasticity for isotropic and anisotropic solids is constructed along the lines of Gudmundson [Gudmundson, P., 2004. A unified treatment of strain-gradient plasticity. J. Mech. Phys. Solids 52, 1379-1406]. Both energetic and dissipative stresses are considered in order to develop a kinematic hardening theory, which in the absence of gradient terms reduces to conventional J₂ flow theory with kinematic hardening. The dissipative stress measures, work-conjugate to plastic strain and its gradient, satisfy a yield condition with associated plastic flow. The theory includes interfacial terms: elastic energy is stored and plastic work is dissipated at internal interfaces, and a yield surface is postulated for the work-conjugate stress quantities at the interface. Uniqueness and extremum principles are constructed for the solution of boundary value problems, for both the rate-dependent and the rate-independent cases. In the absence of strain gradient and interface effects, the minimum principles reduce to the classical extremum principles for a kinematically hardening elasto-plastic solid. A rigid-hardening version of the theory is also stated and the resulting theory gives rise to an extension to the classical limit load theorems. This has particular appeal as previous trial fields for limit load analysis can be used to generate immediately size-dependent bounds on limit loads.