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Micromechanical Design of Carbon Nanotube Ribbon Reinforced Polymer Composite Materials

Lightweight materials are an important component of the design of aerospace structures. Carbon nanotube materials have been considered for this purpose due to the strength and stiffness of individual nanotubes, and the commercial availability of bulk formats such as fibers. These fibers can have a ribbon cross section which results in a different design space for their composites relative to traditional reinforcements which have a round cross section. This work applies brick-and-mortar micromechanical models and classical lamination theory with an inverse approach to investigate the design space of these composites. Using this approach, the influences of fiber geometry and axial and transverse mechanical properties are mapped. Finally, a sensitivity study is performed and the relative impacts of ±10% variations in the constituent material and geometric properties are ranked. Lamina axial moduli were found to range from a maximum of 3x to 1x minimum relative to a target quasi-isotropic laminate modulus depending on the anisotropy and shear modulus of the lamina. The fiber targets depended strongly on the fiber volume fraction in the lamina and the fiber axial modulus target was found to range from 4.8x to 3.2x the quasi-isotropic laminate target. The sensitivity analysis found that the largest driver of performance was the volume fraction, followed by the fiber axial modulus. While bio-based brick-and-mortar composites, such as nacre, can benefit from reinforcement aspect ratios above 10, for carbon nanotube ribbon (or carbon fiber)/polymer composites the sensitivity study indicated that the optimal cross-sectional aspect ratio was relatively smaller, potentially less than three.

Micromechanics

Polyimide/Carbon Nanotube Composite Films for Electrostatic Charge Mitigation

Low color, space environmentally durable polymeric films with sufficient electrical conductivity to mitigate electrostatic charge (ESC) build-up have potential applications on large, deployable, ultra-light weight Gossamer spacecraft as thin film membranes on antennas, solar sails, thermal/optical coatings, multi-layer insulation blankets, etc.. The challenge has been to develop a method to impart robust electrical conductivity into these materials without increasing solar absorptivity (alpha ) or decreasing optical transparency or film flexibility. Since these spacecraft will require significant compaction prior to launch, the film portion of the spacecraft will require folding. The state-of-the-art clear, conductive coating (e.g. indium-tin-oxide, ITO) is brittle and cannot tolerate folding. In this report, doping a polymer with single-walled carbon nanotubes (SWNTs) using two different methods afforded materials with good flexibility and surface conductivities in the range sufficient for ESC mitigation. A coating method afforded materials with minimal effects on the mechanical, optical, and thermo-optical properties as compared to dispersal of SWNTs in the matrix. The chemistry and physical properties of these nanocomposites are discussed.

Smith, Joseph G., Jr.

Monolayer Films of Binary Metal Oxide Nanoparticles for Carbon Nanotube Synthesis

Binary metal oxide nanoparticles (biMO-NPs) combining transition and main-group metals with well-organized atomic architectures have unique potential as robust and economical heterogeneous catalysts. Herein, metal oxide nanoparticles (CoAlxOy) using cobalt and aluminum were synthesized, and their structure, morphology, and chemical composition were investigated using various characterization techniques. The biMO-NPs, which had a Gaussian-type size distribution (∼6 nm), were assembled on plain silicon substrates modified chemically with linker molecules bearing suitable end groups. Surface analysis revealed an ordered, uniform, close-packed arrangement of biMO-NPs forming a monolayer architecture with nanoscale thickness (∼12 nm), high surface uniformity, and negligible defects. The nanoparticle monolayer film (NP-MF) was employed as a catalyst to grow carbon nanotube (CNT) forests via the thermal chemical vapor deposition (CVD) method, similar to those grown from catalyst thin films deposited by physical vapor deposition. Structural characterization confirmed the growth of a dense, uniform, high-quality vertically aligned carbon nanotube (VA-CNT) forest with a length of ∼125 µm, which is comparable to the VA-CNTs grown from expensive thin films. Thus, CNT growth was successfully catalyzed by the biMO-NPs, highlighting a simple and inexpensive alternative for catalyst deposition. In this innovative wet-chemistry approach, the catalyst and catalyst support are combined within a single nanoparticle before NP-MF assembly. Interestingly, this approach provides a scalable and cost-effective pathway for CNT growth, eliminating the need for expensive thin deposition techniques.

Regmi, Bishow [University of Cincinnati]

Dirac Fermions and Flat Bands in Phosphorus Carbide Nanotubes: Structural and Quantum Phase Transitions in a Quasi-One-Dimensional Material

Chemically realistic quasi-one-dimensional (1D) materials in which Dirac Fermions and highly degenerate flat bands coexist intrinsically at the Fermi level are exceedingly rare, while representing a highly desirable platform for correlated and topological quantum phenomena. Here, in this work, using specialized symmetry-adapted first-principles calculations we predict a new class of nanomaterials─phosphorus carbide nanotubes (P 2 C 3 NTs)─obtained by rolling monolayer P 2 C 3 , a two-dimensional material shown in a previous letter to host “double Kagome bands”. Both armchair and zigzag P 2 C 3 NTs are stable at room temperature and feature the rare coexistence of Dirac crossings and multiple flat bands at the Fermi level inherited from the underlying honeycomb–Kagome lattice, with the flat bands resilient to elastic deformations. Under large strain, the structure transforms from honeycomb–Kagome to “brick-wall”, accompanied by multiple coupled structural and quantum phase transitions. We also uncover localized edge states, spin splitting from vacancies and dopants, and strain-tunable magnetism. Together, these results establish P 2 C 3 NTs as a chemically specific and mechanically tunable 1D material platform with potential applications in quantum hardware and spintronics.

carbon nanotubes

An Ultra-long Life, High-performance, Flexible Li-CO2Battery Based on Multifunctional Carbon Electrocatalysts

Integrating CO2 utilization and renewable energy delivery/storage, the rechargeable Li–CO2 battery has been considered as a promising candidate for next-generation secondary batteries. However, high-performance catalyst(s) for efficient formation and decomposition of the discharge product, Li2CO3, are an imperative part of a Li–CO2 battery. The development of flexible Li–CO2 batteries extends their applications into compliant and wearable devices/systems, but at the same time imposes a big challenge for battery fabrication and lifetime enhancement. In this study, a rechargeable quasi-solidus flexible Li–CO2 battery was designed and fabricated using highly active N,S-doped carbon nanotubes (N,S-doped CNTs) as the cathode catalyst, and a smart polymer gel as the flexible electrolyte. This newly-developed flexible Li–CO2 battery exhibited a capacity as high as 23560 mAh g−1 based on the catalyst mass and an ultra-long lifetime of up to 538 cycles with excellent mechanical flexibility. This work provides a platform for the design and development of high-performance flexible Li–CO2 batteries from low-cost, earth-abundant, carbon-based multifunctional cathode catalysts.

Superior stability

High Temperature Pressure (HTP) Boron Nitride Nanotube (BNNT): Discovery and Commercialization

Future NASA missions for space exploration require key technological elements that must provide sustainability, survivability and operational envelope in extreme environments, such as the high and low extremes in pressures and temperatures, ionizing radiations, chemical and/or physical corrosion, and hypervelocity particles. Advanced multifunctional materials enable revolutionary design schemes for future aerospace vehicles and structures for the extreme environments of NASA missions. Recent studies of nanocomposite materials have shown the potential for both structural integrity and multifunctional capabilities, such as sensing, actuating, health monitoring, radiation shielding, energy harvesting, thermal management, and thermal protection in extreme environments. After the advent of carbon nanotube (CNT) in 1991, scientists predicted that boron and nitrogen, carbons immediate neighbors on the periodic chart, might also form perfect nanotubes, namely boron nitride nanotubes (BNNTs). The discovery and progress of a new catalyst-free method for synthesizing highly crystalline, very long, and small diameter BNNTs under a high temperature and pressure (HTP) environment have enabled new applications for multifunctional materials. The white color BNNTs offer extraordinary properties including neutron radiation shielding, piezoelectricity, electrostriction, high thermal oxidative stability (>800C in air), not present in CNTs, as well as excellent mechanical strength and toughness, equivalent to CNTs. The characteristics of the BNNTs and their composites along with CNT composites are discussed in this presentation along with their potential aerospace applications in extreme environments.

Cheol Park

Remote-Contact Catalysis for Target-Diameter Semiconducting Carbon Nanotube Arrays

Electrostatic catalysis has been an exciting development in chemical synthesis (beyond enzymes catalysis1 ) in recent years, boosting reaction rates and selectively producing certain reaction products2 . Most of the studies to date have been focused on using external electric field (EEF) to rearrange the charge distribution in small molecule reactions such as Diels-Alder addition3 , carbene reaction4 , etc. However, in order for these EEFs to be effective, a field on the order of 1 V/nm (10 MV/cm) is required, and the direction of the EEF has to be aligned with the reaction axis5 . Such a large and oriented EEF will be challenging for large-scale implementation, or materials growth with multiple reaction axis or steps. Here, we demonstrate that the energy band at the tip of an individual single-walled carbon nanotube6 (SWCNT) can be spontaneously shifted in a high-permittivity growth environment, with its other end in contact with a low-work function electrode (e.g., hafnium carbide or titanium carbide7 ). By adjusting the Fermi level at a point where there is a substantial disparity in the density of states (DOS) between semiconducting (s-) and metallic (m-) SWCNTs8 , we achieve effective electrostatic catalysis for s-SWCNT growth assisted by a weak EEF perturbation (200V/cm). This approach enables the production of high-purity (99.92%) s-SWCNT horizontal arrays with narrow diameter distribution (0.95±0.04 nm), targeting the requirement of advanced SWCNT-based electronics for future computing9-11. These findings highlight the potential of electrostatic catalysis in precise materials growth, especially for s-SWCNTs, and pave the way for the development of advanced SWCNT-based electronics12.

Wang, Jiangtao [Department of Electrical Engineeri

Fullerenes, PAH, Carbon Nanostructures, and Soot in Low Pressure Diffusion Flames

The formation of fullerenes C 60 and C 7O is known to occur in premixed laminar benzene/oxygen/argon flames operated at reduced pressures. High resolution transmission electron microscopy (HRTEM) images of material collected from these flames has identified a variety of multishelled nanotubes and fullerene 'onions' as well as some trigonous structures. These fullerenes and nanostructures resemble the material that results from commercial fullerene production systems using graphite vaporization. As a result, combustion is an interesting method for fullerenes synthesis. If commercial scale operation is to be considered, the use of diffusion flames might be safer and less cumbersome than premixed flames. However, it is not known whether diffusion flames produce the types and yields of fullerenes obtained from premixed benzene/oxygen flames. Therefore, the formation of fullerenes and carbon nanostructures, as well as polycyclic aromatic hydrocarbons (PAH) and soot, in acetylene and benzene diffusion flames is being studied using high performance liquid chromatography (HPLC) and high resolution transmission electron microscopy (HRTEM).

William J Grieco

A Study of Space Environment Effect on Highly Thermally Conductive Hybrid Carbon Fiber Polymer Composites

A set of novel highly thermally conductive hybrid carbon fiber (CF) polymer composites has been developed for lightweight thermal radiator applications in space missions. This study investigates the effects of the space environment on these materials following exposure in low-Earth orbit (LEO) during the Materials International Space Station Experiment (MISSE)-17 flight mission, where samples experienced 159 days of combined atomic oxygen (AO), ultraviolet (UV) radiation, high vacuum, space radiation and thermal cycling. Post-flight characterization included weight loss, surface morphology, thermo-optical properties, molecular structures, glass transition temperature, thermal degradation and thermal conductivity analyses. The pyrolytic graphite sheet (PGS) samples exhibited negligible weight loss, stable thermo-optical property, and only minor oxidation signature on the exposed surface. Although AO erosion of the epoxy polymer matrix was evident, carbon nanotube (CNT)-infused PGS/CF epoxy composites retained high thermal emissivity and preserved their high thermal conductivities. These results demonstrate that the novel highly thermally conductive hybrid CF composites possess strong environmental resilience and are promising candidates for lightweight thermal radiators and thermal management components in future space exploration missions.

Space Environment

Lyotropic Liquid Crystalline Phase Behavior of Boron Nitride Nanotube Aqueous Dispersions

Boron nitride nanotubes (BNNTs) are gaining significant interest due to their outstanding mechanical and thermal properties, as well as their potential to serve as a model nanorod system. Processing BNNT liquid crystalline (LC) dispersions enables precise control over BNNT orientation in macroscopic assemblies, while their low absorption in the visible spectrum facilitates studying LCs at exceptionally high concentrations. Here, we investigate the behavior of BNNTs in aqueous solutions stabilized by the surfactant sodium deoxycholate (SDC), examining the effect of BNNT purity and BNNT−SDC concentrations on lyotropic LC formation. We disperse up to 15wt% BNNT in SDC solutions and use polarized light microscopy to detail the transition from an isotropic state to a biphasic regime, where isotropic and nematic domains coexist due to phase separation, to a single fully nematic phase. Cryogenic electron microscopy provides direct evidence of BNNT alignment within nematic domains. Our results show that enhanced depletion-induced attractions, driven by increased surfactant concentration, lower the threshold concentration of BNNT required to form nematic domains. In contrast, low surfactant concentrations relative to BNNT result in insufficiently coated nanotube surfaces, leading to poor dispersions and BNNT aggregation. Additionally, we fabricate well-aligned BNNT films from aqueous LC dispersions. Our findings advance the understanding of BNNT LCs, offering insight into controlling their orientation and highlighting their potential for high-performance materials.

Joe Khoury

High-density Boron Nitride Nanotube Composites via Surfactant-stabilized Lyotropic Liquid Crystals for Enhanced Space Radiation Shielding

Despite significant technological advancements in space exploration, human space travel and colonization remain limited by the health risks associated with space radiation. Boron nitride nanotubes (BNNTs) have been proposed as an advanced material for space applications due to their high specific strength and efficient radiation shielding capabilities. However, the practical implementation of BNNTs has been slow, primarily due to technological challenges in fabricating structural materials incorporating BNNTs. In this study, a method is presented for fabricating high-density BNNT films that are mechanically robust, exhibit high thermal conductivity, and effectively attenuate space radiation. The key advancement enabling high-density BNNT films is the successful preparation of BNNT liquid crystals (LCs), achieved through the strategic use of a commercial dodecylbenzenesulfonic acid surfactant. This surfactant ensures exceptional BNNT stability in aqueous dispersion, even at concentrations exceeding the LC phase transition threshold. Simulations, estimating the equivalent radiation dose to the human body in space, indicate that a high-density BNNT film with a surface density of 50 g cm−2 reduces the total dose equivalent rate by 56% compared to zero shielding. This enhancement would allow astronauts to extend their mission duration on the lunar surface by a factor of two.

Young-Kyeong Kim

Electromagnetic Melt Processing: A Pathway to New Additive Manufacturing Technologies for Functional High-Performance Thermoplastics

In this study, we apply the electromagnetic (EM) melt processing of thermoplastics on an innovative EM field-driven powder bed fusion additive manufacturing (AM) concept for high-performance functional parts: Selective Microwave Melting/Sintering (SMM/SMS). This technique leverages the EM susceptibility of carbon nanotube-coated polymer micro-pellets to achieve rapid, localized heating and powder fusion. Thus, selective microwave melting (SMM) was used to fabricate multilayer specimens made of recycled polyphenylene sulfide (rPPS) and carbon nanotubes (CNTs). The resulting SMM specimens exhibited very good interlayer integrity, localized fusion at pellet boundaries, and tolerable residual porosity, indicating effective fusion and acceptable consolidation. CNT-rich interphases were retained after irradiation, generating anisotropic electrically active network pathways and enabling conductivity enhancement at low filler content. At only 1.0 wt% CNT, the specimens exhibited electrical conductivity approximately three orders of magnitude higher than neat rPPS. Dynamic mechanical analysis showed improved viscoelastic response relative to neat rPPS, while tensile testing confirmed that the SMM-processed specimens retained practical mechanical integrity despite localized voids. These results demonstrate that SMM can effectively consolidate EM susceptible thermoplastic powder beds while preserving their segregated conductive networks. This may become a scalable route for producing multifunctional thermoplastic parts with low filler loadings, tunable anisotropy, and structured materials and parts. Overall, the findings suggest that EM field-based AM can help overcome key limitations of conventional thermoplastic processing by enabling scalable, energy-efficient fabrication of nanostructured composites and expanding AM to a broader range of resins, including high-performance thermoplastics with customized functional properties.

Powder bed fusion

Development of in-situ polymerized intrinsically conductive resin and low-cost carbon pigments offering high conductivity for sensing, EMI shielding and lighting protection

Electrically conductive composites are emerging across diverse industries such as electronic, automotive, aerospace, advanced air mobility, biomedical, infrastructure, defense and security offering static charge dissipation, electromagnetic interference shielding, lighting protection, sensing, dicing, corrosion monitoring, etc. Conductivity enhanced composites provide several advantages compared to conventional metals including weight reduction, corrosion resistance, energy efficient processability, tunable properties and multifunctionality. Polymers are typically insulating in nature and require conducting filler for electron transport. However, dispersion and polymer-filler interphases are critical and often disrupt conducting pathways. Besides, conductive fillers such as graphene, carbon nanotube, MXene, silver nanowire, etc. are expensive, limiting their wide adoption in composite industry. On the other hand, a limited number of intrinsically conductive polymers are available among which polyaniline (PANI) has been widely studied due to its high conductivity, thermal and chemical stability. However, PANI is difficult to process and exhibits weak mechanical properties. In brief, there is a significant demand for electrically conductive polymer formulation with cost-effective conducting fillers that offer processability in scale to expand the market of conductivity enhanced materials.

Kumar, Vipin [Oak Ridge National Laboratory (ORNL)

Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here, in this work, we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C–Cl bond breaking, which does not involve protons—a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

Choi, Chungseok [Yale Univ., New Haven, CT (United

Interface-induced fast Li+ transport in mixed ionic–electronic conductors

Interfacial instability between lithium metal and solid-state electrolytes limits the performance of all-solid-state lithium metal batteries (ASSLBs), leading to parasitic reactions, non-uniform Li+ flux, and dendrite growth. Here, we develop a composite interlayer composed of the anti-perovskite Li2OHCl0.75Br0.25 (AP) and carbon nanotubes (CNTs) to enhance both interfacial stability and ionic transport. The AP–CNT interlayer exhibits enhanced Li+ conductivity arising from interfacial electron transfer from AP to CNTs, which generates a built-in electric field that facilitates Li+ migration. Lithium symmetric cells incorporating this interlayer achieve a high critical current density of 2.4 mA cm−2 at 55 °C. This design integrates chemical robustness with coupled ion–electron transport, offering a generalizable strategy for safe, dendrite-free, and high-performance ASSLBs.

He, Chenche

Dual atom catalysts for rapid electrochemical reduction of CO to ethylene

Strong CO adsorption and facile CO dimerization are the key challenges in electrochemical CO2 reduction towards multi-carbon (C2+) products. We recently showed that CoPc immobilized on a single-walled carbon nanotube can selectively reduce CO2 to methanol. This is enabled through molecular strain, which dramatically improves the CO adsorption energy to CoPc, which in turn facilitates methanol formation. We now examine the extended Phthalocyanine (PcEx) dual atom catalyst (DAC), which is intrinsically strained and contains two catalyst centers, making it a candidate for reducing CO to C2+ products. Using Quantum Mechanics (QM), we screened 20 elements embedded in the PcEx, seeking catalysts with weak hydrogen binding, strong CO binding, and facile CO dimerization. We identi>ied Fe, Ru, Co, and Ir as the best performers and subsequently evaluated the entire CO to C2H4 mechanism (9 steps) using each of these elements as catalysts. In terms of limiting potential and overall exergonicity, we identi>ied CoPcEx as the best catalyst, followed by IrPcEx. We then examined the full CO to C2H4 mechanism on the bimetallic IrCoPcEx catalyst using grand canonical QM to obtain the reaction energetics as a function of applied potential. We conclude that the bimetallic IrCoPcEx is most promising for ef>iciently converting CO to ethylene.

Musgrave, Charles B.