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Polymer-derived pyrolytic carbons (PyCs) are highly desirable building blocks for high-strength low-density ceramic meta-materials, and reinforcement with nanofibers is of interest to address brittleness and tailor multi-functional properties. The properties of carbon nanotubes (CNTs) make them leading candidates for nanocomposite reinforcement, but how CNT confinement influences the structural evolution of the PyC matrix is unknown. Here, the influence of aligned CNT proximity interactions on nano- and mesoscale structural evolution of phenol-formaldehyde-derived PyCs is established as a function of pyrolysis temperature (Tₚ) using X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy. Aligned CNT PyC matrix nanocomposites are found to evolve faster at the mesoscale by plateauing in crystallite size at Tₚ ∼ 800°C, which is more than 200°C below that of unconfined PyCs. Since the aligned CNTs used here exhibit ∼ 80 nm average separations and ∼ 8 nm diameters, confinement effects are surprisingly not found to influence PyC structure on the atomic-scale at Tₚ ≤ 1400°C. Since CNT confinement could lead to anisotropic crystallite growth in PyCs synthesized below ∼ 1000°C, and recent modeling indicates that more slender crystallites increase PyC hardness, these results inform fabrication of PyC-based meta-materials with unrivaled specific mechanical properties., National Science Foundation (U.S.). Research Experience for Undergraduates (Program) (grant number DMR-08-19762), Massachusetts Institute of Technology. Materials Processing Center, United States. Department of Defense (National Defense Science & Engineering Graduate Fellowship (NDSEG) Program), Airbus Group, Boeing Company, Embraer, Lockheed Martin, Saab (Firm), ANSYS, Inc., Hexcel (Firm), Toho Tenax Co., Ltd. (MIT’s Nano-Engineered Composite aerospace STructures (NECST) Consortium)

Poly(urethane-urea) (PUU) has been infused into ultrahigh volume fraction carbon nanotube (CNT) forests using a heat-curable polymer formula. Polymer nanocomposites with carbon nanotube volume-fractions of 1%, 5%, 10%, 20%, and 30% were fabricated by overcoming densification and infusion obstacles. These polymer nanocomposites were nanoindented quasi-statically and dynamically to discern process-structure-(mechanical) property relations of polymerizing PUU in such densely-packed CNT forests. A 100× increase in indentation modulus has been observed, which is attributed not only to CNT reinforcement of the matrix, but also to molecular interactions in the matrix itself. Quasi-static elastic moduli ranging from 10 MPa–4.5 GPa have been recorded. Storage modulus for all materials is found to track well at loadings of 200 Hz, with little effect observed from increasing CNT volume fraction. Keywords: carbon nanotubes; polymer nanocomposites; polyurethane urea; self-assembly, United States. Army Research Office (Contract W911NF-13-D-0001)

Capillary-mediated densification is an inexpensive and versatile approach to tune the application-specific properties and packing morphology of bulk nanofiber (NF) arrays, such as aligned carbon nanotubes. While NF length governs elasto-capillary self-assembly, the geometry of cellular patterns formed by capillary densified NFs cannot be precisely predicted by existing theories. This originates from the recently quantified orders of magnitude lower than expected NF array effective axial elastic modulus (E), and here we show via parametric experimentation and modeling that E determines the width, area, and wall thickness of the resulting cellular pattern. Both experiments and models show that further tuning of the cellular pattern is possible by altering the NF-substrate adhesion strength, which could enable the broad use of this facile approach to predictably pattern NF arrays for high value applications., United States. National Aeronautics and Space Administration (Grant NNX17AJ32G)

Thin-ply carbon fiber laminates have exhibited superior mechanical properties, including higher initiation and ultimate strength, when compared to standard thickness plies and enable greater flexibility in laminate design. However, the increased ply count in thin-ply laminates also increases the number of ply-ply interfaces, thereby increasing the number of relatively weak and delamination-prone interlaminar regions. In this study, we report the first experimental realization of aligned carbon nanotube interlaminar reinforcement of thin-ply unidirectional prepreg-based carbon fiber laminates, in a hierarchical architecture termed ‘nanostitching’. We synthesize a baseline effective standard thickness laminate using multiple thin-plies of the same orientation to create a ply block, and we find an ∼15% improvement in the interlaminar shear strength via short beam shear (SBS) testing for thin-ply nanostitched samples when compared to the baseline. This demonstrates a synergetic strength effect of nanostitching (∼5% increase) and thin-ply lamination (∼10% increase). Synchrotron-based computed tomography of post mortem SBS specimens suggests a different damage trajectory and mode of damage accumulation in nanostitched thin-ply laminates, notably the complete suppression of delaminations in the nanostitched region. Finite element predictions of damage progression highlight the complementary nature of positive thin-ply and nanostitching effects that are consistent with an ∼15% improvement in Modes I and II interlaminar fracture toughness due to the aligned carbon nanotubes at the thin-ply interfaces. Keywords: Thin-ply laminate; Carbon nanotube; Mechanical properties; Finite element analysis

The promise of enhanced performance has motivated the study of one dimensional nanomaterials, especially aligned carbon nanotubes (A-CNTs), for the reinforcement of polymeric materials. While early work has shown that CNTs have remarkable theoretical properties, more recent work on aligned CNT polymer matrix nanocomposites (A-PNCs) have reported mechanical properties that are orders of magnitude lower than those predicted by rule of mixtures. This large difference primarily originates from the morphology of the CNTs that reinforce the A-PNCs, which have significant local curvature commonly referred to as waviness, but are commonly modeled using the oversimplified straight column geometry. Here we used a simulation framework capable of analyzing 105 wavy CNTs with realistic stochastic morphologies to study the influence of waviness on the compliance contribution of wavy A-CNTs to the effective elastic modulus of A-PNCs, and show that waviness is responsible for the orders of magnitude over-prediction of the A-PNC effective modulus by existing theoretical frameworks that both neglect the shear deformation mechanism and do not properly account for the CNT morphpology. Additional work to quantify the morphology of A-PNCs in three dimensions and simulate their full elastic constitutive relations is planned., Airbus Group, Boeing Company, EMBRAER, Lockheed Martin, Saab (Firm), Toho Tenax Co., Ltd., ANSYS, Inc., NECST Consortium, United States. Army Research Office (Contract W911NF-07-D-0004 and W911NF- 13-D-0001), United States. Air Force Research Laboratory (Contract FA8650-11-D-58000), American Society for Engineering Education. National Defense Science and Engineering Graduate Fellowship

The broader adoption of composite materials in next-generation aerospace architectures is currently limited by the geometrical constraints and high energy costs of traditional manufacturing techniques of PMCs such as autoclave and vacuum-bag-only oven curing techniques. Here, an in situ curing technique for PMCs using a resistive heating film comprised of an aligned carbon nanotube (A-CNT) network is presented. A carbon fiber reinforced plastic (CFRP) prepreg system is effectively cured via a single-side CNT network heater incorporated on the outer surface of the laminate without using an autoclave. Evaluation of the curing efficacy shows that composites cured by A-CNT film heaters can achieve degrees of cure that are equivalent or better than composites cured by an autoclave. This manufacturing technique enables highly efficient curing of PMCs while adding multifunctionality to finished composites., United States. Army Research Office (contract W911NF-07-D-0004), United States. Army Research Office (contract W91NF-13-D-0001), Kwanjeong Educational Foundation (Korea), National Defense Science and Engineering Graduate (NDSEG) Fellowship, Conselho Nacional de Pesquisas (Brazil) (Science without Borders Program), United States. Naval Sea Systems Command (contract N00024-12-P-4069 for SBIR topic N121-058)

The energy losses and geometric constraints associated with conventional curing techniques of polymeric systems motivate the study of a highly scalable out-of-oven curing method using a nanostructured resistive heater comprised of aligned carbon nanotubes (A-CNT). The experimental results indicate that, when compared to conventional oven based techniques, the use of an “out-of-oven” A-CNT integrated heater leads to orders of magnitude reductions in the energy required to process polymeric layered structures such as composites. Integration of this technology into structural systems enables the in situ curing of large-scale polymeric systems at high efficiencies, while adding sensing and control capabilities., United States. Army Research Office (Contract W911NF-07-D-0004), United States. Army Research Office (Contract W911NF-13-D-0001)

We demonstrate the layer-by-layer (LbL) assembly of polyelectrolyte multilayers (PEM) on three-dimensional nanofiber scaffolds. High porosity (99%) aligned carbon nanotube (CNT) arrays are photolithographically patterned into elements that act as textured scaffolds for the creation of functionally coated (nano)porous materials. Nanometer-scale bilayers of poly(allylamine hydrochloride)/poly(styrene sulfonate) (PAH/SPS) are formed conformally on the individual nanotubes by repeated deposition from aqueous solution in microfluidic channels. Computational and experimental results show that the LbL deposition is dominated by the diffusive transport of the polymeric constituents, and we use this understanding to demonstrate spatial tailoring on the patterned nanoporous elements. A proof-of-principle application, microfluidic bioparticle capture using N-hydroxysuccinimide-biotin binding for the isolation of prostate-specific antigen (PSA), is demonstrated., National Science Foundation (U.S.) (Award DMR-0819762)

The flow interception efficiency, which provides a measure of the fraction of streamlines that intercept a porous collector, is an important parameter in applications such as particle capture, filtration, and sedimentation. In this work, flow permeation through a porous circular cylinder located symmetrically between two impermeable parallel plates is investigated numerically under different flow and geometrical conditions. A flow interception efficiency is defined and calculated based on the flow permeation rate for a wide range of system parameters. The dependencies on all physical variables can be captured in three dimensionless numbers: the Reynolds number, the Darcy number (ratio of permeability to the square of cylinder diameter), and the plate separation relative to the cylinder size. The flow interception efficiency is very low in the limit of unbounded cylinders but significantly increases by restricting the flow domain. The fluid permeation rate through the porous cylinder varies nonlinearly with the relative plate/cylinder spacing ratio, especially when the gap between the cylinder and the confining plates is small compared to the cylinder size. In general, the effects of the Reynolds number, the Darcy number, and confinement on the flow interception efficiency are coupled; however, for most practical cases it is possible to factorize these effects. For practical ranges of the Darcy number (Da<10[superscript −4], which means that the pore size is at least one order of magnitude smaller than the porous cylinder diameter), the interception efficiency varies linearly with Da, is independent of the Reynolds number at low Reynolds numbers (Re[subscript D]<10), and varies linearly with Reynolds number at higher flow rates. In addition to numerical solutions, theoretical expressions are developed for the flow interception efficiency in two limiting cases of confined and unbounded flow, based on modeling the system as a network of hydrodynamic resistances, which, National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762), Massachusetts Institute of Technology. Department of Mechanical Engineering (Rohsenow Fellowship)

Intrinsic and scale-dependent properties of carbon nanotubes (CNTs) have led aligned CNT architectures to emerge as promising candidates for next-generation multifunctional applications. Enhanced operating regimes motivate the study of CNT-based aligned nanofiber carbon matrix nanocomposites (CNT A-CMNCs). However, in order to tailor the material properties of CNT A-CMNCs, porosity control of the carbon matrix is required. Such control is usually achieved via multiple liquid precursor infusions and pyrolyzations. Here we report a model that allows the quantitative prediction of the CNT A-CMNC density and matrix porosity as a function of number of processing steps. The experimental results indicate that the matrix porosity of A-CMNCs comprised of ∼1% aligned CNTs decreased from ∼61% to ∼55% after a second polymer infusion and pyrolyzation. The model predicts that diminishing returns for porosity reduction will occur after 4 processing steps (matrix porosity of ∼51%), and that >10 processing steps are required for matrix porosity <50%. Using this model, prediction of the processing necessary for the fabrication of liquid precursor derived A-CMNC architectures, with possible application to other nanowire/nanofiber systems, is enabled for a variety of high value applications., National Science Foundation (U.S.) (Grant CMMI-1130437)

Materials comprising carbon nanotube (CNT) aligned nanowire (NW) polymer nanocomposites (A-PNCs) are emerging as next-generation materials for use in aerospace structures. Enhanced operating regimes, such as operating temperatures, motivate the study of CNT aligned NW ceramic matrix nanocomposites (A-CMNCs). Here we report the synthesis of CNT A-CMNCs through the pyrolysis of CNT A-PNC precursors, thereby creating carbon matrix CNT A-CMNCs. Characterization reveals that the fabrication of high strength, high temperature, lightweight next-generation aerospace materials is possible using this method. Additional characterization and modeling are planned.

The landmark theoretical properties of low dimensional materials have driven more than a decade of research on carbon nanotubes (CNTs) and related nanostructures. While studies on isolated CNTs report behavior that aligns closely with theoretical predictions, studies on cm-scale aligned CNT arrays (>10[superscript 10] CNTs) oftentimes report properties that are orders of magnitude below those predicted by theory. Using simulated arrays comprised of up to 105 CNTs with realistic stochastic morphologies, we show that the CNT waviness, quantified via the waviness ratio (w), is responsible for more than three orders of magnitude reduction in the effective CNT stiffness. Also, by including information on the volume fraction scaling of the CNT waviness, the simulation shows that the observed non-linear enhancement of the array stiffness as a function of the CNT close packing originates from the shear and torsion deformation mechanisms that are governed by the low shear modulus (∼1 GPa) of the CNTs., Massachusetts Institute of Technology. Nano-engineered Composite aerospace STructures (NECST) Consortium, United States. Army Research Office (Contract W911NF-07-D-0004), United States. Army Research Office (Contract W911NF-13-D-0001), United States. Dept. of Defense. National Defense Science & Engineering Graduate Fellowship Program

Here we report the synthesis of graphene oxide nanoscrolls (GONS) with tunable dimensions via low and high frequency ultrasound solution processing techniques. GONS can be visualized as a graphene oxide (GO) sheet rolled into a spiral-wound structure and represent an alternative to traditional carbon nano-morphologies. The scrolling process is initiated by the ultrasound treatment which provides the scrolling activation energy for the formation of GONS. The GO and GONS dimensions are observed to be a function of ultrasound frequency, power density, and irradiation time. Ultrasonication increases GO and GONS C–C bonding likely due to in situ thermal reduction at the cavitating bubble–water interface. The GO area and GONS length are governed by two mechanisms; rapid oxygen defect site cleavage and slow cavitation mediated scission. Structural characterization indicates that GONS with tube and cone geometries can be formed with both narrow and wide dimensions in an industrial-scale time window. This work paves the way for GONS implementation for a variety of applications such as adsorptive and capacitive processes., United States. Dept. of Defense (National Defense Science and Engineering Graduate Fellowship (NDSEG) Program), United States. Army Research Office (contract W911NF-07-D-0004), National Science Foundation (U.S.) (NSF award number ECS-0335765)

Existing theories for quantifying the morphology of nanofibers (NFs) in aligned arrays either neglect or assume a simple functional form for the curvature of the NFs, commonly known as the NF waviness. However, since such assumptions cannot adequately describe the waviness of real NFs, errors that can exceed 10% in the predicted inter-NF separation can result. Here we use a theoretical framework capable of simulating >10[superscript 5] NFs with stochastic three-dimensional morphologies to quantify NF waviness on an easily accessible measure of the morphology, the inter-NF spacing, for a range of NF volume fractions. The presented scaling of inter-NF spacing with waviness is then used to study the morphology evolution of aligned carbon nanotube (A-CNT) arrays during packing, showing that the effective two-dimensional coordination number of the A-CNTs increases much faster than previously reported during close packing, and that hexagonal close packing can successfully describe the packing morphology of the A-CNTs at volume fractions greater than 40 vol%., Massachusetts Institute of Technology. Nano-engineered Composite aerospace STructures (NECST) Consortium, United States. Army Research Office (Contract W911NF-07-D-0004), United States. Army Research Office (Contract W911NF-13-D-0001), United States. Dept. of Defense. National Defense Science & Engineering Graduate Fellowship Program

Carbon nanotube (CNT) reinforced polymers are next-generation, high-performance, multifunctional materials with a wide array of promising applications. The successful introduction of such materials is hampered by the lack of a quantitative understanding of process–structure–property relationships. These relationships can be developed only through the detailed characterization of the nanoscale reinforcement morphology within the embedding medium. Here, we reveal the three-dimensional (3D) nanoscale morphology of high volume fraction (Vf) aligned CNT/epoxy-matrix nanocomposites using energy-filtered electron tomography. We present an automated phase-identification method for fast, accurate, representative rendering of the CNT spatial arrangement in these low-contrast bimaterial systems. The resulting nanometer-scale visualizations provide quantitative information on the evolution of CNT morphology and dispersion state with increasing Vf, including network structure, CNT alignment, bundling and waviness. The CNTs are observed to exhibit a nonlinear increase in bundling and alignment and a decrease in waviness as a function of increasing Vf. Our findings explain previously observed discrepancies between the modeled and measured trends in bulk mechanical, electrical and thermal properties. The techniques we have developed for morphological quantitation are applicable to many low-contrast material systems., Airbus Group, Boeing Company, EMBRAER, Lockheed Martin, Saab (Firm), Hexcel (Firm), Toho Tenax, ANSYS, Inc., NECST Consortium

Here, we quantify the electron transport properties of aligned carbon nanotube (CNT) networks as a function of the CNT length, where the electrical conductivities may be tuned by up to 10× with anisotropies exceeding 40%. Testing at elevated temperatures demonstrates that the aligned CNT networks have a negative temperature coefficient of resistance, and application of the fluctuation induced tunneling model leads to an activation energy of ≈14 meV for electron tunneling at the CNT-CNT junctions. Since the tunneling activation energy is shown to be independent of both CNT length and orientation, the variation in electron transport is attributed to the number of CNT-CNT junctions an electron must tunnel through during its percolated path, which is proportional to the morphology of the aligned CNT network., United States. Army Research Office (contract W911NF-07-D-0004), United States. Army Research Office (contract W911NF-13-D-0001), United States. Air Force Office of Scientific Research (AFRL/RX contract FA8650-11-D-5800, Task Order 0003), National Science Foundation (U.S.) (NSF Award No. ECS-0335765), United States. Dept. of Defense (National Defense Science and Engineering Graduate Fellowship)

By excluding metals from synthesis, growth of carbon nanostructures via unreduced oxide nanoparticle catalysts offers wide technological potential. We report new observations of the mechanisms underlying chemical vapor deposition (CVD) growth of fibrous carbon nanostructures from zirconia nanoparticles. Transmission electron microscope (TEM) observation reveals distinct differences in morphological features of carbon nanotubes and nanofibers (CNTs and CNFs) grown from zirconia nanoparticle catalysts versus typical oxide-supported metal nanoparticle catalysts. Nanofibers borne from zirconia lack an observable graphitic cage consistently found with nanotube-bearing metal nanoparticle catalysts. We observe two distinct growth modalities for zirconia: (1) turbostratic CNTs 2–3 times smaller in diameter than the nanoparticle localized at a nanoparticle corner, and (2) nonhollow CNFs with approximately the same diameter as the nanoparticle. Unlike metal nanoparticle catalysts, zirconia-based growth should proceed via surface-bound kinetics, and we propose a growth model where initiation occurs at nanoparticle corners. Utilizing these mechanistic insights, we further demonstrate that preannealing of zirconia nanoparticles with a solid-state amorphous carbon substrate enhances growth yield., United States. Army Research Office (Contract W911NF-13-D-0001)

Here we present a study on the presence of physisorbed water on the surface of aligned carbon nanotubes (CNTs) in ambient conditions, where the wet CNT array mass can be more than 200% larger than that of dry CNTs, and modeling indicates that a water layer >5 nm thick can be present on the outer CNT surface. The experimentally observed nonlinear and non-monotonic dependence of the mass of adsorbed water on the CNT packing (volume fraction) originates from two competing modes. Physisorbed water cannot be neglected in the design and fabrication of materials and devices using nanowires/nanofibers, especially CNTs, and further experimental and ab initio studies on the influence of defects on the surface energies of CNTs, and nanowires/nanofibers in general, are necessary to understand the underlying physics and chemistry that govern this system., National Science Foundation (U.S.) (NSF Grant No. CMMI-1130437), National Science Foundation (U.S.) (NSF Award Number ECS-0335765), United States. Army Research Office (contract W911NF-07-D-0004)

Ice protection systems (IPS) are critical components for many aerospace flight vehicles, including commercial transports and unmanned aerial systems (UAS), and can include anti-icing, de-icing, ice sensing, etc. Here, an IPS is created using nanomaterials to create a surface-modified external layer on an aerosurface based on observations that polymer nanocomposites have tailorable and attractive heating properties. The IPS uses Joule heating of aligned carbon nanotube (CNT) arrays to create highly efficient de-icing and anti-icing of aerosurfaces. An ice wind tunnel test of a CNT enhanced aerosurface is performed to demonstrate the system under a range of operating regimes (temperature, wind speed, water content in air) including operation down to -20.6°C (-5°F) at 55.9 m/s (125 mph) under heavy icing. Manufacturing, design considerations, and further improvements to the materials and systems are discussed., United States. Dept. of the Navy. Small Business Innovation Research (Contract N68335-11-C-0424), National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Grant DMR-0819762)