Thermoelectric behavior of aerogels based on graphene and multi-walled carbon nanotube nanocomposites

In this work, we presented that the Seebeck coefficient and electrical conductivity can be increased simultaneously in aerogels based on graphene and multi-walled carbon nanotube (graphene-MWCNT) nanocomposites, and at the same time the thermal conductivity is depressed due to 3D porous skeleton structure. As a result, graphene-MWCNT aerogels possess ultra-low thermal conductivities (∼0.056 W m⁻¹ K⁻¹) and apparent density (∼24 kg m⁻³), thereafter the figure of merit (ZT) of ∼0.001 is achieved. Although the ZT value is too low for practical application as a thermoelectric (TE) material, the unique structure in this project provides a potential way to overcome the challenge in bulk semiconductors that increasing electrical conductivity generally leads to decreased Seebeck coefficient and enhanced thermal conductivity.     

Single-wall carbon nanotube coating on a pyroelectric detector

Carbon single-wall nanotubes (SWNTs) are studied as the thermal-absorption coating on a large area pyroelectric detector. The SWNTs were produced by a laser vaporization method and dispersed onto the detector surface by use of a simple airbrush technique. The detector was based on a 1-cm-diameter, 60-microm-thick lithium tantalate disk having nickel electrodes. We report the spectral responsivity of the detector ranging from 600 to 1800 nm, as well as the spatial and directional uniformity at 850 nm. Using Drude and Lorentzian dielectric functions and an effective medium approximation to obtain the indices of refraction of semiconductor and metallic SWNTs, we compared the expected theoretical relative responsivity for the two types of tube with the measured relative responsivity of the detector. Values of thermal conductivity, specific heat, and damage threshold obtained from the literature are compared with properties of alternatives for thermal coatings such as gold-black and carbon-based paint.     

Tensile and fatigue behavior of superelastic shape memory rods

The tensile and fatigue behavior of superelastic shape memory alloy (SMA) bars heat-treated at three different temperatures were examined. Low cycle fatigue tests at variable load rates were carried out to determine the effect of stress and frequency on residual strain and energy dissipation in a fatigue cycle. The mechanism of energy dissipation was studied by monitoring the temperature changes in the fatigued samples as a function of applied stress and frequency of testing. Results from the tensile tests revealed that the stress for the Austenite to Martensite transformation decreased from 408 MPa to 204 MPa with an increase in temperature of heat treatment from 300 to 450 °C. The ultimate strength of the SMA increased from 952 MPa to 1115 MPa when the heat treatment temperature was increased from 300 to 450 °C. Fatigue testing prior to conducting the tensile test decreased the ultimate strength of the SMA and also reduced the failure strain. The energy dissipation in fatigue tests was found to decrease as test frequency increased from 0.025 Hz to 0.25 Hz and the change in sample temperature during the test at the lower test frequency was found to be considerably higher than at the higher frequency.     

Aligned carbon nanotube coating on polyethylene surface formed by microwave radiation

Multifunctional carbon nanotube (CNT) architectures have been created on polyethylene (PE) surface by a microwave welding process. The continuous and aligned CNT films drawn from super-aligned CNT arrays can significantly absorb microwave energy and act as a network of nanosized thermal sources to locally melt the PE substrate beneath, leading to polymer wrapping around individual nanotubes. Uniform and highly conductive CNT/PE nanocomposite layer was formed without undermining the original alignment of the CNTs. CNT patterns have also been precisely fabricated on PE samples. The PE/CNT/PE bonds showed high interfacial strengths, which were affected by the duration of microwave radiation. With ultra-low content of CNTs introduced as antistatic agents, the dissipation of surface charges on PE substrate has been tremendously improved.     

Multi-composition oxidation resistant coating for SiC-coated carbon/carbon composites at high temperature

This work proposes a multi-composition oxidation resistant coating for SiC-coated carbon/carbon (C/C) composites by slurry method using the mixture of Y₂O₃, ZrO₂, Al₂O₃, Si and C. XRD analysis shows that the phases of the composite coating are composed of SiC, Al₂O₃, Y₂O₃, ZrO₂, Al₄SiC₄ and Y₃Al₂(AlO₄)₃. SEM analysis of the cross section of the coating displays the microstructure with 500 μm thickness which filled the porous SiC. Oxidation test shows that, after 19 h oxidation in air at 1873 K, the weight loss of the coated SiC-C/C is only 1.76%. The oxidation of the coated C/C composites was primarily due to the reaction of C/C matrix and oxygen diffusing through the penetrable cracks and bubble holes in the coating.     

Efficient coating of transparent and conductive carbon nanotube thin films on plastic substrates

Optically transparent and electrically conductive single-walled carbon nanotube (SWNT) thin films were fabricated at room temperature using a dip-coating technique. The film transparency and sheet resistance can be easily tailored by controlling the number of coatings. Aminopropyltriethoxysilane (APTS) was used as an adhesion promoter and, together with surfactant Triton X-100, greatly improved the SWNTs coating. Only five coats were required to obtain a sheet resistance of 2.05?[Formula: see text] and film transparency of 84?%T. The dip-coated film after post-deposition treatment with nitric acid has a sheet resistance as low as 130?[Formula: see text] at 69?%T. This technique is suitable for large-scale SWNT coating at room temperature and can be used on different types of substrates such as glass and plastics. This paper will discuss the role of the adhesion promoter and surfactant in the coating process.     

Infrared responsivity of a pyroelectric detector with a single-wall carbon nanotube coating

The performance of a 10 mm diameter pyroelectric detector coated with a single-wall carbon nanotube (SWCNT) was evaluated in the 0.8 to 20 microm wavelength range. The relative spectral responsivity of this detector exhibits significant fluctuations over the wavelength range examined. This is consistent with independent absorbance measurements, which show that SWCNTs exhibit selective absorption bands in the visible and near-infrared. The performance of the detector in terms of noise equivalent power and detectivity in wavelength regions of high coating absorptivity was comparable with gold-black-coated pyroelectric detectors based on 50 microm thick LiTaO(3) crystals. The response of this detector was shown to be nonlinear for DC equivalent photocurrents >10(-9) A, and its spatial uniformity of response was comparable with other pyroelectric detectors utilizing gold-black coatings. The nonuniform spectral responsivity exhibited by the SWCNT-coated detector is expected to severely restrict the use of SWCNTs as black coatings for thermal detectors. However, the deposition of SWCNT coatings on a pyroelectric crystal followed by the study of the prominence of the spectral features in the relative spectral responsivity of the resultant pyroelectric detectors is shown to provide an effective method for quantifying the impurity content in SWCNT samples.     

蒸镀碳化铪(HfC)对单根碳纳米管场致发射性能的改善

采用双向电泳法,在原子力显微镜探针尖端组装了单根碳纳米管,在真空环境下对比测量了单根碳纳米管蒸镀低逸出功材料HfC前后场致发射电流曲线和电流噪声的特点。证明了HfC蒸镀在碳纳米管上能够显著降低发射体的逸出功,减少电流噪声,并且观察到单根碳纳米管蒸镀了HfC后7μA左右的稳定电流发射。通过分析电流噪声,认为碳纳米管场致发射噪声主要来自吸附气体的频繁吸附和脱附。在低电流下,空间电离的离子轰击发射体表面,对吸附状态的影响占主导地位。当单根碳纳米管的场致发射电流超过1μA量级以后,碳纳米管表面温度快速升高,温度对气体吸附的影响占主导地位,吸附的气体分子逐渐脱附后,电流噪声开始降低。     

Surface coating of multi-walled carbon nanotube nanopaper on shape-memory polymer for multifunctionalization

We are presenting a method of synthesizing three-dimensional self-assembled multi-walled carbon nanotube (MWCNT) nanopaper on hydrophilic polycarbonate membrane. The process is based on the very well-defined dispersion of nanotube and controlled pressure vacuum deposition procedure. The morphology and structure of the nanopaper are characterized with scanning electronic microscopy (SEM) over a wide range of scale sizes. A continuous and compact network observed from the microscopic images indicates that the MWCNT nanopaper could have highly conductive property. As a consequence, the sensing properties of conductive MWCNT nanopaper are characterized by functions of temperature and water content. Meanwhile, in combination with shape-memory polymer (SMP), the conductive MWCNT nanopaper facilitates the actuation in SMP nanocomposite induced by electrically resistive heating. Furthermore, the actuating capability of SMP nanocomposite is utilized to drive up a 5-gram mass from 0 to 30 mm in height.     

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.     

Transforming an intrinsically hydrophilic polymer to a robust self-cleaning superhydrophobic coating via carbon nanotube surface embedding

A single-step method, including surface embedding of nanoparticles into a polymer matrix, was employed to fabricate superhydrophobic thermoplastic polyurethane (TPU)/carbon nanotube (CNT) nanocomposite coatings. The main aim was to prove that surface roughness plays a more important role in designing superhydrophobic surfaces as compared with the surface energy. Therefore, TPU was used as the model hydrophilic polymer and CNTs were employed as non-hydrophobic nanoparticles. It was found that, at a certain pressing time, CNTs form an efficient hair-like morphology which is able to highly enclose air within its as-formed pores leading to superhydrophobic behavior. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and confocal microscopy were utilized for characterization of samples. SEM and confocal microscopy results proved that surface roughness played the key role in the final wettability behavior. Based on XPS results, it was also found that a very long pressing time led to partial migration of TPU macromolecules into the CNTs' pores, and hence, superhydrophobicity was reduced. The effects of mechanical abrasion and nanoparticle type on wettability behavior of samples were evaluated as well. In conclusion, it is suggested that surface roughness factor should be highly considered in designing superhydrophobic nanocomposite coatings rather than surface energy.     

Spray coating of carbon nanotube on polyethylene terephthalate film for touch panel application

From a technical perspective, the major limiting factors for the wide adoption of CNT films are the DC conductivity, uniformity of sheet resistance and good adhesion of CNT on film substrate. In this study, the effects of sonificator and process time on the zeta potential and sheet resistance of the CNT-PET film show that although the dispersing power of horn-type sonificator is stronger than that of bath-type, the SWCNT solution obtained with horn-type sonificator agglomerates faster. Likewise, it has been noted that the SWCNT solutions with low enough zeta potentials exhibit higher sheet resistance after making CNT-PET films due to the damage to SWCNTs caused by high dispersion force. Since the spray coating of SWCNT solution gives the SWCNT-SDS composite layer on PET film after drying, the excess SDS should be washed off. The removal of excess SDS was conducted by dipping in the 3 N HNO3 and SOCl2 solution and washing with deionized water followed by heat treatment in a 120 degrees C convection oven for 30 min. The lift-off of SWCNT-SDS composite layer after 40 min dipping in the 3 N HNO3 solution appeared to be due to the continued permeation leading to swelling of the SDS layer by the 3 N HNO3 aqueous solution. It was found that ten times of spray coating cycle gave CNT-PET film the sheet resistance of 310 Ω/[square] and transmittance of 81%. The TSP made with CNT-PET film exhibited a performance equal to the one made with ITO-PET film.     

Stress concentration effect on the fatigue properties of carbon nanotube/epoxy composites

This study experimentally investigates the stress concentration effect on the fatigue properties of multi-walled nanotube (MWCNT)/epoxy nanocomposites by employing the dumbbell type specimens with central through-hole notches. Both the hole sizes and the CNT contents are considered as the experimental variables. The experimental results show that the fatigue strengths of the notched nanocomposites decrease with an increase in hole sizes. The notch sensitivity factors increase with the notch root radii and the ultimate strengths of the nanocomposite specimens. This study employed a mathematical model to relate the notch sensitivity with the hole size and a material constant, and this employed material constant was found to depend on the ultimate strength rather than the CNT contents of the nanocomposites.     

A nonlinear mechanical model for the fatigue life of thin-film carbon nanotube supercapacitors

The effects of cyclic loading on the mechanical performance and fatigue life of a novel carbon nanotube supercapacitor are investigated. The highly flexible supercapacitor is a monolithic, pre-fabricated, fully functional film made of a nanostructured free-standing layer in which ions are stored within two vertically aligned multi-walled carbon nanotube (MWCNs) electrodes that are monolithically interspaced by a solution of microcrystalline cellulose in a room temperature ionic liquid electrolyte. To study the cyclic mechanical response of such nanostructured multilayer composite, an original framework is adopted by combining the equivalent continuum approach of Eshelby–Mory–Tanaka and a Weibull-like approach for the evolution of debonding carbon nanotubes electrodes. One- and three-layer models of the supercapacitor are proposed. Cyclic tests are numerically carried out in strain control. A fatigue life limit is determined by considering a confidence interval for the number of cycles corresponding to the states at which the effective elastic modulus of the partially debonded nanostructured portion of the supercapacitor is reduced by a percentage between 20% and 30%. The simulated cyclic tests yield Wholer-type fatigue curves showing the fatigue life limit as the maximum number of cycles N for each strain amplitude.The sensitivity of the fatigue life with respect to meaningful parameters such as the interfacial strength between the MWCNs and cellulose is investigated. Frequency-response functions of the multilayer nanostructured composite are further computed as function of the strain amplitude during cyclic tests.     

炭气凝胶及其有机气凝胶前驱体的吸附性能

间苯二酚和糠醛的醇溶液在六次甲基四胺催化下经溶胶-凝胶过程合成醇凝胶,常压干燥后得到有机气凝胶,经炭化获得炭气凝胶.利用TEM和N2吸附表征了炭气凝胶及其有机气凝胶前驱体的结构,并通过有机蒸汽吸附实验研究了气凝胶的结构-吸附性能关系.实验结果表明：有机气凝胶和炭气凝胶对极性有机蒸汽的静态饱和吸附量高于对非极性有机蒸汽的静态饱和吸附量;提高热处理温度,有利于气凝胶对低浓度极性有机蒸汽和各种浓度非极性有机蒸汽的吸附,但不利于对高浓度极性有机蒸汽的吸附;随着有机蒸汽浓度的提高,气凝胶对极性有机蒸汽的吸附量明显增大,但对非极性有机蒸汽的吸附量影响不大,仅略微上升.此外,气凝胶的室温脱附率高达60 %～85 %.     

Effect of fibre coating and geometry on the tensile properties of hybrid carbon nanotube coated carbon fibre reinforced composite

Hierarchically structured hybrid composites are ideal engineered materials to carry loads and stresses due to their high in-plane specific mechanical properties. Growing carbon nanotubes (CNTs) on the surface of high performance carbon fibres (CFs) provides a means to tailor the mechanical properties of the fibre–resin interface of a composite. The growth of CNT on CF was conducted via floating catalyst chemical vapor deposition (CVD). The mechanical properties of the resultant fibres, carbon nanotube (CNT) density and alignment morphology were shown to depend on the CNT growth temperature, growth time, carrier gas flow rate, catalyst amount, and atmospheric conditions within the CVD chamber. Carbon nanotube coated carbon fibre reinforced polypropylene (CNT-CF/PP) composites were fabricated and characterized. A combination of Halpin–Tsai equations, Voigt–Reuss model, rule of mixture and Krenchel approach were used in hierarchy to predict the mechanical properties of randomly oriented short fibre reinforced composite. A fractographic analysis was carried out in which the fibre orientation distribution has been analyzed on the composite fracture surfaces with Scanning Electron Microscope (SEM) and image processing software. Finally, the discrepancies between the predicted and experimental values are explained.     

The effect of carbon nanotube dimensions and dispersion on the fatigue behavior of epoxy nanocomposites

Fatigue is one of the primary reasons for failure in structural materials. It has been demonstrated that carbon nanotubes can suppress fatigue in polymer composites via crack-bridging and a frictional pull-out mechanism. However, a detailed study of the effects of nanotube dimensions and dispersion on the fatigue behavior of nanocomposites has not been performed. In this work, we show the strong effect of carbon nanotube dimensions (i.e.?length, diameter) and dispersion quality on fatigue crack growth suppression in epoxy nanocomposites. We observe that the fatigue crack growth rates can be significantly reduced by (1) reducing the nanotube diameter, (2) increasing the nanotube length and (3) improving the nanotube dispersion. We qualitatively explain these observations by using a fracture mechanics model based on crack-bridging and pull-out of the nanotubes. By optimizing the above parameters (tube length, diameter and dispersion) we demonstrate an over 20-fold reduction in the fatigue crack propagation rate for the nanocomposite epoxy compared to the baseline (unfilled) epoxy.     

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.     

Enhancement of delamination fatigue resistance in carbon nanotube reinforced glass fiber/polymer composites

We show that the addition of small volume fractions of multi-walled carbon nanotubes (CNTs) to the matrix of glass–fiber composites reduces cyclic delamination crack propagation rates significantly. In addition, both critical and sub-critical inter-laminar fracture toughness values are increased. These results corroborate recent experimental evidence that the incorporation of CNTs improve fatigue life by a factor of two to three in in-plane cyclic loading. We show that in both the critical and sub-critical cases, the degree of delamination suppression is most pronounced at lower levels of applied cyclic strain energy release rate, ΔG. High-resolution scanning electron microscopy of the fracture surfaces suggests that the presence of the CNTs at the delamination crack front slows the propagation of the crack due to crack bridging, nanotube fracture, and nanotube pull-out. Further examination of the sub-critical fracture surfaces shows that the relative proportion of CNT pull-out to CNT fracture is dependent on the applied cyclic strain energy, with pull-out dominating as ΔG is reduced. The conditions for crack propagation via matrix cracking and nanotube pull-out and fracture are studied analytically using fracture mechanics theory and the results compared with data from the experiments. It is believed that the shift in the fracture behavior of the CNTs is responsible for the associated increase in the inter-laminar fracture resistance that is observed at lower levels of ΔG relative to composites not containing CNTs.