Juan J. Vilatela

High-Performance Carbon Nanotube Fiber

With their impressive individual properties, carbon nanotubes should form high-performance fibers. We explored the roles of nanotube length and structure, fiber density, and nanotube orientation in achieving optimum mechanical properties. We found that carbon nanotube fiber, spun directly and continuously from gas phase as an aerogel, combines high strength and high stiffness (axial elastic modulus), with an energy to breakage (toughness) considerably greater than that of any commercial high-strength fiber. Different levels of carbon nanotube orientation, fiber density, and mechanical properties can be achieved by drawing the aerogel at various winding rates. The mechanical data obtained demonstrate the considerable potential of carbon nanotube assemblies in the quest for maximal mechanical performance. The statistical aspects of the mechanical data reveal the deleterious effect of defects and indicate strategies for future work.

A Model for the Strength of Yarn-like Carbon Nanotube Fibers

A model for the strength of pure carbon nanotube (CNT) fibers is derived and parametrized using experimental data and computational simulations. The model points to the parameters of the subunits that must be optimized in order to produce improvements in the strength of the macroscopic CNT fiber, primarily nanotube length and shear strength between CNTs. Fractography analysis of the CNT fibers reveals a fibrous fracture surface and indicates that fiber strength originates from resistance to nanotube pull-out and is thus proportional to the nanotube-nanotube interface contact area and shear strength. The contact area between adjacent nanotubes is determined by their degree of polygonization or collapse, which in turn depends on their diameter and number of layers. We show that larger diameter tubes with fewer walls have a greater degree of contact, as determined by continuum elasticity theory, molecular mechanics, and image analysis of transmission electron micrographs. According to our model, the axial stress in the CNTs is built up by stress transfer between adjacent CNTs through shear and is thus proportional to CNT length, as supported by data in the literature for CNT fibers produced by different methods and research groups. Our CNT fibers have a yarn-like structure in that rather than being solid, they are made of a network of filament subunits. Indeed, the model is consistent with those developed for conventional yarn-like fibers.

Yarn-Like Carbon Nanotube Fibers

Supplementary on-line Material SOM 1: Numerical Equivalence Between Specific Stress in Units of GPa/SG and N/tex Units of Specific Stress and Specific Stiffness are used in Materials Science in situations where there is a premium on weight reduction. To account for the unit weight of material, the conventional stress ( =F/A), is divided by the volumetric density of the material (’ = /V ). Typically however, specific gravity (SG) is used instead of volumetric density so as to preserve the dimensionality of the units of stress. Furthermore, one can see that this specific stress (’) is equivalent to normalising the load bearing capacity of the material by its mass per unit length (i. e. by its linear density, L):

Strong Dependence of Mechanical Properties on Fiber Diameter for Polymer−Nanotube Composite Fibers: Differentiating Defect from Orientation Effects

We have prepared polyvinylalcohol-SWNT fibers with diameters from ∼1 to 15 μm by coagulation spinning. When normalized to nanotube volume fraction, V(f), both fiber modulus, Y, and strength, σ(B), scale strongly with fiber diameter, D: Y/V(f) ∝ D(-1.55) and σ(B)/V(f) ∝ D(-1.75). We show that much of this dependence is attributable to correlation between V(f) and D due to details of the spinning process: V(f) ∝ D(0.93). However, by carrying out Weibull failure analysis and measuring the orientation distribution of the nanotubes, we show that the rest of the diameter dependence is due to a combination of defect and orientation effects. For a given nanotube volume fraction, the fiber strength scales as σ(B) ∝ D(-0.29)D(-0.64), with the first and second terms representing the defect and orientation contributions, respectively. The orientation term is present and dominates for fibers of diameter between 4 and 50 μm. By preparing fibers with low diameter (1-2 μm), we have obtained mean mechanical properties as high as Y = 244 GPa and σ(B) = 2.9 GPa.

Liquid Infiltration into Carbon Nanotube Fibers: Effect on Structure and Electrical Properties

Carbon nanotube (CNT) fibers consist of a network of highly oriented carbon nanotube bundles. This paper explores the ingress of liquids into the contiguous internal pores between the bundles using measurements of contact angles and changes in fiber dimensions. The resultant effects on the internal structure of the fiber have been examined by WAXS and SAXS. A series of time-resolved experiments measured the influence of the structural changes on the electrical resistivity of the fiber. All organic liquids tested rapidly wicked into the fiber to fill its internal void structure. The local regions in which the nanotube bundles are aggregated to give a bundle network were broken up by the liquid ingress. For the range of organic penetrants examined, the strength of the effects on structure and electrical resistivity was correlated, not only with the degree to which the liquid reduced the nanotube surface energy, but also with the Hansen affinity parameters. The fact that liquid environments influence the electrical performance of these fibers is of significance if they are to replace copper as power and signal conductors, with added implications regarding the possible ingress of external insulating materials, and possibly also sensing applications.

Strong Carbon Nanotube Fibers by Drawing Inspiration from Polymer Fiber Spinning

We present a method to spin highly oriented continuous fibers of adjustable carbon nanotube (CNT) type, with mechanical properties in the high-performance range. By lowering the concentration of nanotubes in the gas phase, through either reduction of the precursor feed rate or increase in carrier gas flow rate, the density of entanglements is reduced and the CNT aerogel can thus be drawn (up to 18 draw ratio) and wound at fast rates (>50 m/min). This is achieved without affecting the synthesis process, as demonstrated by Raman spectroscopy, and implies that the parameters controlling composition in terms of CNT diameter and number of layers are decoupled from those fixing CNT orientation. Applying polymer fiber wet-spinning principles then, strong CNT fibers (1 GPa/SG) are produced under dilute conditions and high draw ratios, corresponding to highly aligned fibers (from wide- and small-angle X-ray scattering). This is demonstrated for fibers either made up of predominantly single-wall CNTs (SWCNTs) or predominantly multiwall CNTs (MWCNTs), which surprisingly have very similar tensile properties. Finally, we show that postspin densification has no substantial effect on either alignment or properties (mechanical and electrical). These results demonstrate a route to control CNT assembly and reinforce their potential as a high-performance fiber.

Tuning the Mechanical Properties of Composites from Elastomeric to Rigid Thermoplastic by Controlled Addition of Carbon Nanotubes

A commercial thermoplastic polyurethane is identified for which the addition of nanotubes dramatically improves its mechanical properties. Increasing the nanotube content from 0% to 40% results in an increase in modulus, Y, (0.4-2.2 GPa) and stress at 3% strain, σ(ϵ = 3%) , (10-50 MPa), no significant change in ultimate tensile strength, σ(B) , (≈50 MPa) and decreases in strain at break, ϵ(B) , (555-3%) and toughness, T, (177-1 MJ m(-3) ). This variation in properties spans the range from compliant and ductile, like an elastomer, at low mass fractions to stiff and brittle, like a rigid thermoplastic, at high nanotube content. For mid-range nanotube contents (≈15%) the material behaves like a rigid thermoplastic with large ductility: Y = 1.5 GPa, σ(ϵ = 3%) = 36 MPa, σ(B) = 55 MPa, ϵ(B) = 100% and T = 50 MJ m(-3) . Analysis suggests that soft polyurethane segments are immobilized by adsorption onto the nanotubes, resulting in large changes in mechanical properties.

Structural composites for multifunctional applications: Current challenges and future trends

Abstract This review paper summarizes the current state-of-art and challenges for the future developments of fiber-reinforced composites for structural applications with multifunctional capabilities. After a brief analysis of the reasons of the successful incorporation of fiber-reinforced composites in many different industrial sectors, the review analyzes three critical factors that will define the future of composites. The first one is the application of novel fiber-deposition and preforming techniques together with innovative liquid moulding strategies. The second is the combination of these techniques by optimization tools based on novel multiscale modeling approaches, so fiber-reinforced composites with optimized properties can be designed and manufactured for each application. In addition, the third is the enhancement of composite applications by the incorporation of multifunctional capabilities. Among them, electrical conductivity, energy storage (structural supercapacitors and batteries) and energy harvesting (piezoelectric and solar energy) seem to be the most promising ones.

Structural studies on carbon nanotube fibres by synchrotron radiation microdiffraction and microfluorescence

This study reports on the characterization of a carbon nanotube fibre using synchrotron radiation microbeam small- and wide-angle X-ray scattering in combination with microfluorescence. The fibre, spun directly from a chemical vapour deposition reaction zone, is imaged in terms of microstructural heterogeneities. The results reveal a fibre consisting of highly oriented nanotube bundles and unoriented carbonaceous material. Within the oriented component there is a variable orientation distribution and evidence of differences in nanotube packing. Single catalyst crystallites can be located within the fibre from their wide-angle X-ray scattering signal, and the particulate distribution imaged using X-ray microfluorescence. Whilst this study only constitutes a preliminary analysis, it demonstrates the application of existing fibre characterization methods to new materials. It also highlights the potential of synchrotron radiation micro- and nanobeam small- and wide-angle X-ray scattering and microfluorescence for the study of fibres of a few µm diameter.

Highly responsive UV-photodetectors based on single electrospun TiO2 nanofibres

In this work we study the optoelectronic properties of individual TiO2 fibres produced through coupled sol–gel and electrospinning, by depositing them onto pre-patterned Ti/Au electrodes on SiO2/Si substrates. Transport measurements in the dark give a conductivity above 2 × 10−5 S, which increases up to 8 × 10−5 S in vacuum. Photocurrent measurements under UV-irradiation show high sensitivity (responsivity of 90 A W−1 for 375 nm wavelength) and a response time to illumination of ∼5 s, which is superior to state-of-the-art TiO2-based UV photodetectors. Both responsivity and response speed are higher in air than in vacuum, due to oxygen adsorbed on the TiO2 surface which traps photoexcited free electrons in the conduction band, thus reducing the recombination processes. The photodetectors are sensitive to light polarization, with an anisotropy ratio of 12%. These results highlight the interesting combination of large surface area and low 1D transport resistance in electrospun TiO2 fibres. The simplicity of the sol–gel/electrospinning synthesis method, combined with a fast response and high responsivity makes them attractive candidates for UV-photodetection in ambient conditions. We anticipate their high (photo) conductance is also relevant for photocatalysis and dye-sensitized solar cells.