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This viewgraph presentation provides information on trends in NASA nanotechnology research and development, and future biotechnological applications for that nanotechnology. The presentation covers nanoelectronics, nanosensors, and nanomaterials, biomimetics, devices and materials for health care, carbon nanotubes, biosensors for astrobiology, solid-state nanopores for DNA sequencing, and protein nanotubes.
The new wave of single wall carbon nanotube (SWCNT) infused composites will yield structurally sound multifunctional nanomaterials. The SWCNT network requires thorough dispersion within the polymer matrix in order to maximize the benefits of the nanomaterial. However, before any nanomaterials can be used in aerospace applications a means of quality assurance and quality control must be certified. Quality control certification requires a means of quantification, however, the measurement protocol mandates a method of seeing the dispersion first. We describe here the new tools that we have developed and implemented to first be able to see carbon nanotubes in polymers and second to measure or quantify the dispersion of the nanotubes.
Carbon nanotube (CNT) related nanostructures possess remarkable electrical, mechanical, and thermal properties. To produce these nanostructures for real world applications, a large-scale controlled growth of carbon nanotubes is crucial for the integration and fabrication of nanodevices and nanosensors. We have taken the approach of integrating nanopatterning and nanomaterials synthesis with traditional silicon micro fabrication techniques. This integration requires a catalyst or nanomaterial protection scheme. In this paper, we report our recent work on fabricating wafer-scale carbon nanotube AFM cantilever probe tips. We will address the design and fabrication considerations in detail, and present the preliminary scanning probe test results. This work may serve as an example of rational design, fabrication, and integration of nanomaterials for advanced nanodevice and nanosensor applications.
MXenes are a relatively new class of nanomaterial consisting of alternating layers of transition metals and carbon or nitrogen, capped off on either end by terminal groups, usually from the P-block. They have been considered for a wide range of purposes, including hydrogen storage. In this study, thermogravimetric analysis and mass spectrometry residual gas analysis are performed on Ti 3 C 2 T x and Ti 2 CT x to characterize their terminal groups. The hydrogen absorption capabilities of the heat-treated samples are measured using a Sievert apparatus and compared against untreated samples. This reveals that, during heating, the MXenes lose hydrogen, water, fluoride, hydrofluoric acid, and carbon dioxide. Isothermal absorption measurements suggest that the removal of termination groups might improve hydrogen uptake kinetics at high temperatures, but has little effect at room temperatures.
The invention is directed to a method for attaching nanomaterials containing hexagonal lattices to polymer surfaces. For example, carbon nanotubes (CNTs) can be attached to polycarbonate, polyethylene, or epoxy surfaces by amination of the polymer surface, functionalization of the surfaces of CNTs with ester groups, and reacting the aminated surface of the polymer with the ester groups of the functionalized surfaces of the CNTs in an organic solvent to chemically bind the CNTs to the polymer surface.
In the two decades since Iijima's report on carbon nanotubes (CNT), there has been great interest in realizing the benefits of mechanical properties observed at the nanoscale in large-scale structures. The weight savings possible due to dramatic improvements in mechanical properties relative to state-of-the-art material systems can be game changing for applications like aerospace vehicles. While there has been significant progress in commercial production of CNTs, major aerospace applications that take advantage of properties offered by this material have yet to be realized. This paper provides a perspective on the technical challenges and barriers for insertion of CNTs as an emerging material technology in aerospace applications and proposes approaches that may reduce the typical timeframe for technology maturation and insertion into aerospace structures.
Nanocomposites containing nanoscale materials offer exciting opportunities to encode nanoscale features into macroscale dimensions, which produces unprecedented impact in material design and application. However, conventional methods cannot process nanocomposites with a high particle loading, as well as nanocomposites with the ability to be tailored at multiple scales. A composite architected mesoscale process strategy that brings particle loading nanoscale materials combined with multiscale features including nanoscale manipulation, mesoscale architecture, and macroscale formation to create spatially programmed nanocomposites with high particle loading and multiscale tailorability is reported. The process features a low-shrinking (<10%) “green-to-brown” transformation, making a near-geometric replica of the 3D design to produce a “brown” part with full nanomaterials to allow further matrix infill. Here, this demonstration includes additively manufactured carbon nanocomposites containing carbon nanotubes (CNTs) and thermoset epoxy, leading to multiscale CNTs tailorability, performance improvement, and 3D complex geometry feasibility. The process can produce nanomaterial-assembled architectures with 3D geometry and multiscale features and can incorporate a wide range of matrix materials, such as polymers, metals, and ceramics, to fabricate nanocomposites for new device structures and applications.
Arsenic pollution of water is one of the severest environmental challenges threatening human health. Iron-based nanomaterials have been demonstrated effective in arsenic removal. However, they generally suffer from low removal efficiency towards highly toxic As(III), loss of active sites owing to agglomeration, and poor reusability. Herein, we report a carbonized melamine foam supported Mn(IV)-doped β-FeOOH nanospindles(CF@Mn-FeOOH NSp) for tackling the technical hurdles. The designed CF@Mn-FeOOH NSp appears as a free-standing monolith through a low-cost and straightforward hydrothermal method. The atomic-scale integration of Mn(IV) into β-FeOOH enables an oxidation-adsorption bifunctionality, where Mn(IV) serves as oxidizer for As(III) and Fe(III) acts as adsorber for As(V). The maximal adsorption capacity for As(V) and As(III) can reach 152 and 107 mg g -1 , respectively. Meanwhile, As in simulated high arsenic groundwater can be decreased to below 10 μg L -1 within 24 h. By simple "filtrating-washing", 85% and 82% of its initial adsorption capacity for As(V) and As(III) can be easily recovered even after 5-cycles reuse. Kinetics and isotherm adsorption study indicate that the arsenic adsorption behavior is mainly through chemical bonding during single-layer adsorbing process. The as-prepared CF@Mn-FeOOH offers a scalable, efficient, and recyclable solution for arsenic removal in groundwater and wastewater from mines and industry.
Composite cryotanks, or composite overwrapped pressure vessels (COPVs), offer advantages over currently used aluminum-lithium cryotanks, particularly with respect to weight savings. Future NASA missions are expected to use COPVs in spaceflight propellant tanks to store fuels, oxidizers, and other liquids for launch and space exploration vehicles. However, reliability, reparability, and reusability of the COPVs are still being addressed, especially in cryogenic temperature applications; this has limited the adoption of COPVs in reusable vehicle designs. The major problem with composites is the inherent brittleness of the epoxy matrix, which is prone to microcrack formation, either from exposure to cryogenic conditions or from impact from different sources. If not prevented, the microcracks increase gas permeation and leakage. Accordingly, materials innovations are needed to mitigate microcrack damage, and prevent damage in the first place, in composite cryotanks. The self-healing technology being developed is capable of healing the microcracks through the use of a novel engineered nanocomposite, where a uniquely designed nanoparticle additive is incorporated into the epoxy matrix. In particular, this results in an enhancement in the burst pressure after cryogenic cycling of the nanocomposite COPVs, relative to the control COPVs. Incorporating a novel, self-healing, epoxy-based resin into the manufacture of COPVs allows repeatable self-healing of microcracks to be performed through the simple application of a low-temperature heat source. This permits COPVs to be reparable and reusable with a high degree of reliability, as microcracks will be remediated. The unique phase-separated morphology that was imparted during COPV manufacture allows for multiple self-healing cycles. Unlike single-target approaches where one material property is often improved at the expense of another, robustness has been introduced to a COPV by a combination of a modified resin and nanoparticle additives. Unique nanoparticles were used that have been surface-functionalized to be compatible with the resin. Both organic and inorganic components toughen the matrix and result in a more impact-resistant COPV. In one resin system containing an inorganic nanomaterial additive, a significant improvement in burst performance was observed after the COPV was cryo-impact-damaged and then self-healed, with a greater than 10% improvement in burst pressure after the self-healing process was performed. Initial cross-sectional analysis via microscopy showed good resin infiltration of the carbon fibers and without voids. To further enhance the capability between the nanomaterial additives and the resin, a surface modification was successfully performed. A second specialty epoxy resin was prepared using a surface modified nanomaterial additive, and COPVs were fabricated. Steps were taken to improve the mechanical properties of the COPVs by using a low-viscosity resin system that contained a different curing agent. This lower viscosity improves the processing of the COPV, and preliminary results show that the burst pressure of these new vessels is 20 to 25% higher than that of the original. The self-healing concept demonstrated in this research and development effort represents a platform technology, and the self-healing property is neither restricted to the particular epoxy system used here, nor to the COPV application. Self-healing is a direct result of a unique phase separated morphology created via the resin and is aided by the nanoparticles. The self-healing function can be introduced to other customer-specific resin systems in coating, bulk, or composite applications provided that the unique phase separated morphology can be enabled in those systems.
Biogeochemical processing of metals including the fabrication of novel nanomaterials from metal contaminated waste streams by microbial cells is an area of intense interest in the environmental sciences. Here we focus on the fate of Ce during the microbial reduction of a suite of Ce-bearing ferrihydrites with between 0.2 and 4.2 mol% Ce. Cerium K-edge X-ray absorption near edge structure (XANES) analyses showed that trivalent and tetravalent cerium co-existed, with a higher proportion of tetravalent cerium observed with increasing Ce-bearing of the ferrihydrite. The subsurface metal-reducing bacterium Geobacter sulfurreducens was used to bioreduce Ce-bearing ferrihydrite, and with 0.2 mol% and 0.5 mol% Ce, an Fe(II)-bearing mineral, magnetite (Fe(II)(III) 2 O 4 ), formed alongside a small amount of goethite (FeOOH). At higher Ce-doping (1.4 mol% and 4.2 mol%) Fe(III) bioreduction was inhibited and goethite dominated the final products. During microbial Fe(III) reduction Ce was not released to solution, suggesting Ce remained associated with the Fe minerals during redox cycling, even at high Ce loadings. In addition, Fe L 2,3 X-ray magnetic circular dichroism (XMCD) analyses suggested that Ce partially incorporated into the Fe(III) crystallographic sites in the magnetite. The use of Ce-bearing biomagnetite prepared in this study was tested for hydrogen fuel cell catalyst applications. Platinum/carbon black electrodes were fabricated, containing 10% biomagnetite with 0.2 mol% Ce in the catalyst. The addition of bioreduced Ce-magnetite improved the electrode durability when compared to a normal Pt/CB catalyst. Different concentrations of Ce can inhibit the bioreduction of Fe(III) minerals, resulting in the formation of different bioreduction products. Bioprocessing of Fe-minerals to form Ce-containing magnetite (potentially from waste sources) offers a sustainable route to the production of fuel cell catalysts with improved performance.
Plasma technology is actively used for nanoparticle synthesis and modification. All plasma techniques share the ambition of providing high quality, nanostructured materials with full control over their crystalline state and functional properties. Pulsed-DC physical/chemical vapour deposition, high power impulse magnetron sputtering, and pulsed cathodic arc are consolidated low-temperature plasma processes for the synthesis of high-quality nanocomposite films in vacuum environment. However, atmospheric arc discharge stands out thanks to the high throughput, wide variety, and excellent quality of obtained stand-alone nanomaterials, mainly core–shell nanoparticles, transition metal dichalcogenide monolayers, and carbon-based nanostructures, like graphene and carbon nanotubes. Unique capabilities of this arc technique are due to its flexibility and wide range of plasma parameters achievable by modulation of the frequency, duty cycle, and amplitude of pulse waveform. The many possibilities offered by pulsed arc discharges applied on synthesis of low-dimensional materials are reviewed here. Periodical variations in temperature and density of the pulsing arc plasma enable nanosynthesis with a more rational use of the supplied power. Parameters such as plasma composition, consumed power, process stability, material properties, and economical aspects, are discussed. Lastly a brief outlook towards future tendencies of nanomaterial preparation is proposed. Atmospheric pulsed arcs constitute promising, clean processes providing ecological and sustainable development in the production of nanomaterials both in industry and research laboratories.
Monitoring of energy infrastructure through robust yet economical sensing platforms is becoming an area of increased importance, with ubiquitous applications including the electrical grid, natural gas and oil transportation pipelines, H2 infrastructure (storage and transportation), carbon storage, power generation, and subsurface environments. Plasmonic and functional nanomaterial enabled fiber optic sensors show excellent promise for a wide range of sensing applications due to their versatility to be engineered for specific analytes of interest while retaining inherent advantages of the optical fiber sensor platform. Through the design of novel sensing layers, the optical transduction mechanism and wavelength dependence can also be tailored for ease of integration with low-cost interrogation systems enabling an inexpensive yet highly functional optical fiber sensing platform. In addition, recent advances in artificial intelligence and machine learning theoretical methods have been leveraged to simultaneously extract multiple parameters through multi-wavelength interrogation such that unique wavelengths can also serve as unique sensing elements, analogous to electronic nose sensor technologies. The concept of an optical fiber based “photonic nose” via multiple interrogation wavelengths and/or sensor nodes offers a compelling platform technology to realize multiparameter speciation of chemical analytes within complex gas mixtures. In this Perspective, we further generalize the notion of multiparameter sensing through the novel “photonic nervous system” concept based upon low-cost, functionalized optical fiber sensor probes monitoring a variety of distinct analyte classes (physical, chemical, electromagnetic, etc.) simultaneously to provide broad situational awareness via integrated sensors.
Over the past 30 years, carbon nanotubes have emerged as one of the most exciting classes of nanomaterials due to their unique physicochemical properties. While challenges in nanotube synthesis and processing initially hindered their adoption, many of these barriers have since been addressed by research and manufacturing advances, resulting in substantial industrial application of nanotubes across multiple sectors. However, much of this progress is not known in the academic community. This perspective discusses the current landscape and outlook of industrial integration of carbon nanotubes and key factors mediating widespread integration across all major material-related areas of human activity.
Transient transformation in plants is a useful process for evaluating gene function. However, there is a scarcity of minimally perturbing methods for gene delivery that can be used on multiple organs, plant species, and non-excised tissues. We pioneered and demonstrated the use of vertically aligned carbon nanofiber (VACNF) arrays to efficiently perform transient transformation of different tissues with DNA constructs in multiple plant species. The VACNFs permeabilize plant tissue transiently to allow molecules into cells without causing a detectable stress response. We successfully delivered DNA into leaves, roots and fruit of five plant species (Arabidopsis, poplar, lettuce, Nicotiana benthamiana , and tomato) and confirmed accumulation of the encoded fluorescent proteins by confocal microscopy. Using this system, it is possible to transiently transform plant cells with both small and large plasmids. The method is successful for species recalcitrant to Agrobacterium -mediated transformation. VACNFs provide simple, reliable means of DNA delivery into a variety of plant organs and species.
The delivery of biomolecules and impermeable dyes to intact plants is a major challenge. Nanomaterials are up-and-coming tools for the delivery of DNA to plants. As exciting as these new tools are, they have yet to be widely applied. Nanomaterials fabricated on rigid substrate (backing) are particularly difficult to successfully apply to curved plant structures. This study describes the process for microfabricating vertically aligned carbon nanofiber arrays and transferring them from a rigid to a flexible substrate. We detail and demonstrate how these fibers (on either rigid or flexible substrates) can be used for transient transformation or dye (e.g., fluorescein) delivery to plants. We show how VACNFs can be transferred from rigid silicon substrate to a flexible SU-8 epoxy substrate to form flexible VACNF arrays. Further, to overcome the hydrophobic nature of SU-8, fibers in the flexible film were coated with a thin silicon oxide layer (2-3 nm). To use these fibers for delivery to curved plant organs, we deposit a 1 µL droplet of dye or DNA solution on the fiber side of VACNF films, wait 10 min, place the films on the plant organ and employ a swab with a rolling motion to drive fibers into plant cells. With this method, we have achieved dye and DNA delivery in plant organs with curved surfaces.
Today, the atmospheric carbon dioxide (CO 2 ) concentration is 421ppm, over one hundred ppm higher than it was at any point in the last 800,000 years (NASA, 2023). Multiple strategies are necessary to reduce the presence of carbon dioxide in the atmosphere. Besides limiting CO 2 output, carbon capture technology is essential to reduce the overall amount of CO 2 . The Microencapsulated CO 2 Sorbents (MECS) team at Lawrence Livermore National laboratory has developed technologies that can capture CO 2 inside microcapsules, where it can be temporarily stored and later released. In 2017, the commercial potential of these microcapsules was recognized. The brewing industry only requires about one third of the CO 2 it releases for carbonization and packaging, which Congwang Ye and Lionel Keene learned when they met with leaders of small breweries in Colorado to discuss employing carbon capture microcapsules in their processes to reduce their carbon footprint and production costs (Thomas, 2017). The breweries were interested in the technology, but the existing microcapsules require hydration, which is an expensive process for small brewers. In order to develop the microcapsules so they can be commercialized, it is essential to reduce their water loss to improve efficiency and reduce costs for the customers. One method to resolve this issue is to alter the membrane formulation by adding a material that is known to be hydrophobic to decrease the water permeability of the entire membrane. The goal of this project was to study the effect of dispersing a nanomaterial in the polymer membrane shells of microcapsules on the water vapor and carbon dioxide permeability of the membranes.
One of the grand challenges that impedes practical applications of nanomaterials is the lack of robust manufacturing methods that are scalable, cheap, and environmentally friendly. In this work, we address this challenge by developing a microfluidic approach that produces surfactant-free Pd nanocrystals (NCs) uniformly loaded on N-doped porous carbon in a one-batch process. The deep eutectic solvent (DES) prepared from choline chloride and ethylene glycol was employed as a novel synthesis solvent, and its extended hydrogen networks and abundant ionic species effectively stabilize Pd facets and confine nanocrystal sizes without using surfactants. The microreactors provide faster heat exchange and more uniform mass transport, which in combination with DES produced Pd NCs with better-defined shape and predominately exposed Pd (100) facet. Furthermore, we describe that the N-doped functional groups in porous carbon direct dense and uniform heterogeneous growth of Pd NCs in a one-batch process, thereby eliminating a separate catalyst deposition step that is often involved in conventional synthesis. The Pd NCs in the one-batch-produced Pd/C catalysts exhibited a size distribution of similar to ~13 ± 3.5 nm and a high ESCA of 46.0 m 2 /g and delivered 362 mA/mg for formic acid electrochemical oxidation with improved stability, demonstrating the unique potentials of microfluidic reactors and DES for the controllable and scalable synthesis of electrocatalyst materials for practical applications.
Nanomaterials activities at NASA-Johnson Space Center focus on single wall carbon nanotube production, characterization and their applications for aerospace. Nanotubes are produced by arc and laser methods and the growth process is monitored by in-situ diagnostics using time resolved passive emission and laser induced fluorescence of the active species. Parametric study of both these processes are conducted to monitor the effect of production parameters including temperature, buffer gas, flow rate, pressure, laser fluence and arc current. Characterization of the nanotube material is performed using the NASA-JSC protocol developed by combining analytical techniques of SEM, TEM, UV-VIS-NIR absorption, Raman, and TGA. Efforts at JSC over the past five years in composites have centered on structural polymernanotube systems. Recent activities broadened this focus to multifunctional materials, supercapacitors, fuel cells, regenerable CO2 absorbers, electromagnetic shielding, radiation dosimetry and thermal management systems of interest for human space flight. Preliminary tests indicate improvement of performance in most of these applications because of the large surface area as well as high conductivity exhibited by SWCNTs.