Water soluble polymer/carbon nanotube bulk heterojunction solar cells

We report the characteristics of polymer/quantum dot solar cells fabricated using a water-soluble polymer and carbon nanotubes in a bulk heterojunction configuration. The water-soluble polythiophene polymer showed significant photoresponse and the potential for use in photovoltaics. The addition of carbon nanotubes to the polymer resulted in an order of magnitude increase in the photoconductivity. Improved charge separation and collection was evidenced by the large difference between light and dark conductivities as well as the increase in both open circuit voltage and short circuit current. Finally, photovoltaic cells using aligned nanotubes showed further improvement in the photoconductivity and IV characteristics.     

On the contribution of carbon nanotube deformation to piezoresistivity of carbon nanotube/polymer composites

The change in electrical resistance due to mechanical deformation of carbon nanotube (CNT)/polymer composites can be rationalized in terms of two effects: (i) changes in the composite electrical resistivity due to changes in the CNT network configuration and (ii) deformation of the CNTs themselves. The contribution of CNT dimensional changes (ii) to the piezoresistivity of CNT/polymer composites is investigated here. An analytical model based exclusively on dimensional changes which describes the CNT change of electrical resistance in terms of its mechanical deformation is proposed. A micromechanics approach and finite element analysis are performed to correlate the macroscale composite strain to the individual CNT strain. The CNT change of electrical resistance is quantified for different matrix elastic moduli and CNT weight fractions. The CNT/polymer composite is also modeled as an effective continuum material in terms of both its electrical and mechanical responses so that the effect of dimensional changes on the global piezoresistivity can be investigated. Based on the modeling predictions and previous experimental results, it is estimated that the CNT change of resistance due to the macroscale composite strain is marginal (∼5%) compared to the total composite change of resistance commonly measured in the laboratory, suggesting that the dominant effect in the piezoresistivity of CNT/polymer composites is the change in the CNT network configuration.     

Fracture behavior of carbon nanotube/carbon microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance composite delamination resistance, and possibly improve toughness. In the present study, aligned CNTs were grown upon carbon fabric via chemical vapor deposition. Continuously monitored single-fiber composite fragmentation tests were performed on pristine and CNT-grafted fibers embedded in epoxy, and single-laminate compact-tension specimens were tested for fracture behavior. A significant increase (up to 20 %) was observed in the interfacial adhesion, at the cost of a decrease in the fiber tensile strength. As a result, the maximum load of the composite was decreased, but its residual load-bearing capacity more than doubled. The likely sources of these effects are discussed, as well as their implications.     

Multilayered carbon nanotube/polymer composite based thermoelectric fabrics

Thermoelectrics are materials capable of the solid-state conversion between thermal and electrical energy. Carbon nanotube/polymer composite thin films are known to exhibit thermoelectric effects, however, have a low figure of merit (ZT) of 0.02. In this work, we demonstrate individual composite films of multiwalled carbon nanotubes (MWNT)/polyvinylidene fluoride (PVDF) that are layered into multiple element modules that resemble a felt fabric. The thermoelectric voltage generated by these fabrics is the sum of contributions from each layer, resulting in increased power output. Since these fabrics have the potential to be cheaper, lighter, and more easily processed than the commonly used thermoelectric bismuth telluride, the overall performance of the fabric shows promise as a realistic alternative in a number of applications such as portable lightweight electronics.     

Quantitative study of the dispersion degree in carbon nanofiber/polymer and carbon nanotube/polymer nanocomposites

Quantitative measurements of the filler dispersion degree of carbon nanofiber (CNF) and nanotube (CNT) reinforced polymer nanocomposites have been made by transmission electron microscopy. Samples were prepared by either high-shear mixing or twin-screw extrusion processing. It was found that the filler dispersion degree was largely influenced by the filler size. As the filler dimension became smaller, the dispersion parameter D_0.1 largely decreased as quantified, which demonstrated the challenges associated with improving the dispersion of smaller fillers. This work provided a method to quantitatively compare the dispersion degrees of CNF/CNT polymer nanocomposites.     

Failure of carbon nanotube/polymer composites and the effect of nanotube waviness

This paper studies the failure of CNT/polymer composites by combining micromechanics model and finite element simulation. A computational model of composite of adequate size is employed so the interactions between nanotubes embedded in the matrix can be taken into account. The effects of nanotube waviness and random nanotube distribution relative to aligned straight nanotubes are investigated. The computational results indicate that the nanotube waviness tend to reduce the elastic modulus but increase the ultimate strain of a composite. The randomness of nanotube distribution tends to reduce both the composite elastic modulus and tensile strength. The damage initiation and evolution in composites with random wavy nanotubes have also been analyzed.     

Efficiently harvesting excitons from electronic type-controlled semiconducting carbon nanotube films

We have employed thin films of highly purified semiconducting carbon nanotubes as near-infrared optical absorbers in heterojunction photovoltaic and photodetector devices with the electron acceptor C(60). In comparison with previous implementations of more electrically heterogeneous carbon nanotube/C(60) devices, we have realized a 10× gain in zero-bias quantum efficiency (QE) and even more substantial gains in power conversion efficiency (η(p)). The semiconducting nanotube/C(60) heterojunctions are highly rectifying with a peak external QE, internal QE, and η(p) of 12.9 ± 1.3, 91 ± 22, and 0.6%, respectively, in the near-infrared. We show that the device efficiency is determined by the effective length scale for exciton migration in the nanotube films, confirm the high internal QE via photoluminescence quenching, and demonstrate that the driving force for exciton dissociation at the fullerene-fullerene heterointerface is optimized for diameters <1.0 nm. These results will guide the development of next-generation high-performance carbon nanotube-based solar cells and photosensitive devices.     

Multiwalled carbon nanotube reinforced polymer composites

Due to their high stiffness and strength, as well as their electrical conductivity, carbon nanotubes are under intense investigation as fillers in polymer matrix composites. The nature of the carbon nanotube/polymer bonding and the curvature of the carbon nanotubes within the polymer have arisen as particular factors in the efficacy of the carbon nanotubes to actually provide any enhanced stiffness or strength to the composite. Here the effects of carbon nanotube curvature and interface interaction with the matrix on the composite stiffness are investigated using micromechanical analysis. In particular, the effects of poor bonding and thus poor shear lag load transfer to the carbon nanotubes are studied. In the case of poor bonding, carbon nanotubes waviness is shown to enhance the composite stiffness.     

碳纳米管填充聚合物复合材料的介电性能研究

本文研究了未经处理的多壁碳纳米管／聚偏氟乙烯（MWNT／PVDF）复合材料体系的介电性能。发现，在低频下，复合材料的介电常数随MWNT的含量增加而迅速增加．当体积分数为2．0％时，介电常数高迭300左右．并且复合材料的渗流闲值仅为1．61％（体积分数）。MWNT较大的长径比和较高的电导率导致复合体系渗流闻值较低。发生渗流效应时，复合材料的介电损耗低于0．4，与频率无关。因此。可以认为未经过化学处理的碳纳米管可以大幅度改善PVDF基复合材料的介电性能。     

Electrospinning carbon nanotube polymer composite nanofibers

The unique and exceptional physical properties of carbon nanotubes have inspired their use as a filler within a polymeric matrix to produce carbon nanotube polymer composites with enhanced mechanical, thermal and electrical properties. A powerful method of synthesising nanofibers comprising these polymer composites is electrospinning, which utilises an applied electric stress to draw out a thin nanometer-dimension fiber from the tip of a sharp conical meniscus. The focussing of the flow due to converging streamlines at the cone vertex then ensures alignment of the carbon nanotubes along the fiber axis, thus enabling the anisotropic properties of the nanotubes to be exploited. We consider the work that has been carried out to date on various aspects encompassing preprocessing, synthesis and characterisation of these electrospun polymer composite nanofibers as well as the governing mechanisms and associated properties of such fibers. Particular attention is also dedicated to the theoretical modelling of these fiber systems, in particular to the electrohydrodynamic modelling of electrospinning polymer jets.     

碳纳米管填充聚合物复合材料的介电性能研究

本文研究了未经处理的多壁碳纳米管/聚偏氟乙烯(MWNT/PVDF)复合材料体系的介电性能.发现,在低频下,复合材料的介电常数随MWNT的含量增加而迅速增加,当体积分数为2.0%时,介电常数高达300左右,并且复合材料的渗流阈值仅为1.61%(体积分数).MWNT较大的长径比和较高的电导率导致复合体系渗流阈值较低.发生渗流效应时,复合材料的介电损耗低于0.4,与频率无关.因此,可以认为未经过化学处理的碳纳米管可以大幅度改善PVDF基复合材料的介电性能.     

High-cycle fatigue of hybrid carbon nanotube/glass fiber/polymer composites

Glass fiber polymer composites have high strength, low cost, but suffer from poor performance in fatigue. Mechanisms for high-cycle (>10⁴ cycles) fatigue failure in glass fiber composites consist primarily of matrix-dominated damage accumulation and growth that coalesce and propagate into the fibers resulting in ultimate fatigue failure. This investigation shows that the addition of small volume fractions of multi-walled carbon nanotubes (CNTs) in the matrix results in a significant increase in the high-cycle fatigue life. Cyclic hysteresis measured over each cycle in real time during testing is used as a sensitive indicator of fatigue damage. We show that hysteresis growth with cycling is suppressed when CNTs are present with resulting longer cyclic life. Incorporating CNTs into the matrix tends to inhibit the formation of large cracks since a large density of nucleation sites are provided by the CNTs. In addition, the increase in energy absorption from the fracture of nanotubes bridging across nanoscale cracks and nanotube pull-out from the matrix is thought to contribute to the higher fatigue life of glass composites containing CNTs. High-resolution scanning electron microscopy suggests possible mechanisms for energy absorption including nanotube pull-out and fracture. The distributed nanotubes in the matrix appear to inhibit damage propagation resulting in overall improved fatigue strength and durability.     

Thickness-dependent thermoelectric power factor of polymer-functionalized semiconducting carbon nanotube thin films

The effects of polymer structures on the thermoelectric properties of polymer-wrapped semiconducting carbon nanotubes have yet to be clarified for elucidating intrinsic transport properties. We systematically investigate thickness dependence of thermoelectric transport in thin films containing networks of conjugated polymer-wrapped semiconducting carbon nanotubes. Well-controlled doping experiments suggest that the doping homogeneity and then in-plane electrical conductivity significantly depend on film thickness and polymer species. This understanding leads to achieving thermoelectric power factors as high as 412 μW m^?1 K^?2 in thin carbon nanotube films. This work presents a standard platform for investigating the thermoelectric properties of nanotubes.     

Modeling the elastic properties of carbon nanotube array/polymer composites

In this work, the elastic properties of single-walled carbon nanotube (SWNT) arrays and their composites are investigated. The properties of twisted SWNT nano-arrays or ropes of circular cross-section are predicted through a finite element analysis by applying proper boundary conditions to the model and using the strain energy method. The nano-array properties are then used to describe the properties of twisted SWNT nano-array/polymer composites. The effect of volume fraction and aspect ratio of the nano-array as reinforcement for dilute polymer composite systems are examined for aligned and random reinforcement distribution using conventional micromechanics. Finally, elastic properties of the twisted SWNT nano-array/polymer composites are compared to the results from constitutive model of individual nanotube-reinforced polymer composites.     

Manufacturing polymer/carbon nanotube composite using a novel direct process

A direct process for manufacturing polymer carbon nanotube (CNT)-based composite yarns is reported. The new approach is based on a modified dry spinning method of CNT yarn and gives a high alignment of the CNT bundle structure in yarns. The aligned CNT structure was combined with a polymer resin and, after being stressed through the spinning process, the resin was cured and polymerized, with the CNT structure acting as reinforcement in the composite. Thus the present method obviates the need for special and complex treatments to align and disperse CNTs in a polymer matrix. The new process allows us to produce a polymer/CNT composite with properties that may satisfy various engineering specifications. The structure of the yarn was investigated using scanning electron microscopy coupled with a focused-ion-beam system. The tensile behavior was characterized using a dynamic mechanical analyzer. Fourier transform infrared spectrometry was also used to chemically analyze the presence of polymer on the composites. The process allows development of polymer/CNT-based composites with different mechanical properties suitable for a range of applications by using various resins.     

Strain-dependent electrical resistance of multi-walled carbon nanotube/polymer composite films

The strain-dependent electrical resistance characteristics of multi-walled carbon nanotube (MWCNT)/polymer composite films were investigated. In this research, polyethylene oxide (PEO) is used as the polymer matrix. Two representative volume fractions of MWCNT/PEO composite films were selected: 0.56?vol% (near the percolation threshold) and 1.44?vol% (away?from the percolation threshold) of MWCNT. An experimental setup which can measure electrical resistance and strain simultaneously and continuously has been developed. Unique and repeatable relationships in resistance versus strain were obtained for multiple specimens with different volume fractions of MWCNT. The overall pattern of electrical resistance change versus strain for the specimens tested consists of linear and nonlinear regions. A resistance change model to describe the combination of linear and nonlinear modes of electrical resistance change as a function of strain is suggested. The unique characteristics in electrical resistance change for different volume fractions imply that MWCNT/PEO composite films can be used as tunable strain sensors and for application into embedded sensor systems in structures.     

Tailoring organic heterojunction interfaces in bilayer polymer photovoltaic devices

In an ideal model, a p-n junction is formed by two stacked slabs of semiconductors. Although the construction of actual devices is generally more complex, we show that such a simple method can in fact be applied to the formation of organic heterojunctions. Two films of the organic semiconductors poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) can be connected by a simple film-transfer method without disturbing their flat surfaces. Each film can further be modified with a surface-segregated monolayer to tune the strength and direction of the surface dipole moment. Using this method, we fabricated bilayer organic photovoltaic devices with interfacial dipole moments that were selected to align the energy levels at the heterojunction. The open-circuit voltages of the P3HT/PCBM devices could be tuned over a wide range between 0.3 and 0.95 V, indicating that, even if the same combination of bulk materials is used, the interfacial properties drastically alter the performance of organic photovoltaic devices.     

Interfacial load transfer in carbon nanotube/ceramic microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance the composite delamination resistance, and possibly improve its toughness and any matrix-dominated elastic property as well. In the present work aligned CNTs were grown upon ceramic fibers (silica and alumina) by chemical vapor deposition (CVD) at temperatures of 650 °C and 750 °C. Continuously-monitored single fiber composite (SFC) fragmentation tests were performed on pristine as well as on CNT-grown fibers embedded in epoxy. The critical fragment length, fiber tensile strength at critical length, and interfacial shear strength were evaluated. Significant increases (up to 50%) are observed in the fiber tensile strength and in the interfacial adhesion (which was sometimes doubled) with all fiber types upon which CNTs are CVD-grown at 750 °C. We discuss the likely sources of these improvements as well as their implications.     

Strain sensing in polymer/carbon nanotube composites by electrical resistance measurement

In this work multiwall carbon nanotubes (MWCNTs) dispersed in a polymer matrix have been used for strain sensing of the resulting nanocomposite under tensile loading. This was achieved by measuring the relative electrical resistance change (ΔR/R₀) in conductive polyvinylidenefluoride (PVDF)/MWCNTs nanocomposites prepared by melt-mixing with varying filler content from 0.5 wt.% to 8 wt.%. Two main parameters were systematically studied. The PVDF/MWCNTs mixing procedure that results in a successful MWCNTs dispersion, and the effect of MWCNTs content on material’s sensing behaviour. The samples were subjected to tensile loading and the longitudinal strain was monitored together with the longitudinal electrical resistance. The results showed that MWCNTs dispersed in insulating PVDF matrix have the potential to be used as a sensitive network to monitor the strain levels in polymer/carbon nanotube nanocomposites as the deformation level of each sample was being reflected by the resistance changes.