Atomistic simulations of dislocation activity in Si nanofibers in Al-Si eutectics
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Materials Science↗
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Oriented nanofibers embedded in a polymer matrix
A method of forming a composite of embedded nanofibers in a polymer matrix is disclosed. The method includes incorporating nanofibers in a plastic matrix forming agglomerates, and uniformly distributing the nanofibers by exposing the agglomerates to hydrodynamic stresses. The hydrodynamic said stresses force the agglomerates to break apart. In combination or additionally elongational flow is used to achieve small diameters and alignment. A nanofiber reinforced polymer composite system is disclosed. The system includes a plurality of nanofibers that are embedded in polymer matrices in micron size fibers. A method for producing nanotube continuous fibers is disclosed. Nanofibers are fibrils with diameters of 100 nm, multiwall nanotubes, single wall nanotubes and their various functionalized and derivatized forms. The method includes mixing a nanofiber in a polymer; and inducing an orientation of the nanofibers that enables the nanofibers to be used to enhance mechanical, thermal and electrical properties. Orientation is induced by high shear mixing and elongational flow, singly or in combination. The polymer may be removed from said nanofibers, leaving micron size fibers of aligned nanofibers.
Barrera, Enrique V.↗
Treated Carbon Nanofibers for Storing Energy in Aqueous KOH
A surface treatment has been found to enhance the performances of carbon nanofibers as electrode materials for electrochemical capacitors in which aqueous solutions of potassium hydroxide are used as the electrolytes. In the treatment, sulfonic acid groups are attached to edge plane sites on carbon atoms. The treatment is applicable to a variety of carbon nanofibers, including fibrils and both single- and multiple-wall nanotubes. The reason for choosing nanofibers over powders and other forms of carbon is that nanofibers offer greater power features. In previous research, it was found that the surface treatment of carbon nanofibers increased energy-storage densities in the presence of acid electrolytes. Now, it has been found that the same treatment increases energy-storage densities of carbon nanofibers in the presence of alkaline electrolytes when the carbon is paired with a NiOOH electrode. This beneficial effect varies depending on the variety of carbon substrate to which it is applied. It has been conjectured that the sulfonic acid groups, which exist in a deprotonated state in aqueous KOH solutions, undergo reversible electro-chemical reactions that are responsible for the observed increases in energystorage capacities. The increases can be considerable: For example, in one case, nanofibers exhibited a specific capacitance of 34 Farads per gram before treatment and 172 Farads per gram (an increase of about 400 percent) after treatment. The most promising application of this development appears to lie in hybrid capacitors, which are devices designed primarily for storing energy. These devices are designed to be capable of (1) discharge at rates greater than those of batteries and (2) storing energy at densities approaching those of batteries. A hybrid capacitor includes one electrode like that of a battery and one electrode like that of an electrochemical capacitor. For example, a hybrid capacitor could contain a potassium hydroxide solution as the electrolyte, a carbon capacitor electrode, and a nickel hydroxide battery electrode. By making the capacitor electrode of treated carbon nanofibers instead of another carbon material, one could obtain greater energy-storage capacity.
Firsich, David W.↗
Facile synthesis of co-doped Carbon nanofibers for supercapacitor applications
Here, in this study, the synthesis and electrochemical performance of carbon nanofibers (CNFs) co-doped with aluminum (Al) and nitrogen (N) and decorated with zinc oxide (ZnO) nanoparticles are investigated. After electrospinning polyacrylonitrile (PAN) nanofibers, the nanofiber mats are coated with Al and ZnO precursors by the dip coating method and converted into carbon nanofibers by thermal treatments at 850 °C. Co-doping and nanoparticle decoration affect the efficacy of carbon nanofibers as supercapacitors. With a maximal specific capacitance of 206.28 Fg -1 , it is believed that our produced carbon nanofibers, which can effectively store the renewable energy resources required to meet the rising energy demand, offer superior electrochemical properties compared to traditional supercapacitor materials. The effective incorporation of Al, N, and ZnO into the CNF structure, in conjunction with enhanced electrochemical performance, represents a significant advancement in the development of functional carbon nanofibers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synthesis and application of thermally responsive nanofiber coatings for overtemperature monitoring
This study presents a one-pot synthesis route to organometallic nanofibers based on copper thiolate, exhibiting distinctive chemical and physical characteristics. Electron microscopy analysis of morphology and composition revealed 2-10 μm-long, 50-90 nm-diameter hollow and non-hollow fibers composed of copper, sulfur, oxygen, hydrocarbon, and chlorine. Thermogravimetric analysis showed a pronounced mass loss within 120°C-135°C. To elucidate the thermal responsive pathways, the nanofibers were characterized before and after heating. X-ray photoelectron spectroscopy indicates that an initially mixed Cu(I)/Cu(II) oxidation states transition to predominantly Cu(I) upon heating. A layer of nanofiber was coated on battery pouch foil and evaluated as a candidate thermally sensitive coating. At elevated temperature (100-130°C), nanofiber coating released volatile organic compounds, sulfide and sulfur dioxide as detected using multiple gas sensors. This thermally responsive gas release/sensing approach provides a potential large-area temperature monitoring strategy, which is particularly relevant where direct temperature measurements of individual batteries is impractical. The results established proof of concept for nanofiber-coated battery pouch foil as overtemperature warning platform that can provide alerts when surface temperatures exceed a critical threshold. More broadly, the ability to form interconnected fiber networks positions copper thiolate nanofiber coatings as promising materials for advanced applications.
Ihala Gamaralalage, Chanaka [ORNL] (ORCID:00000002↗
Electrospinner Upgrades for Nanofiber Production
Electrospinning is an inexpensive and flexible method for producing nanofibers. Nanofibers are highly adaptable with potential applications in accelerator target systems, air and water filtration, and biomedicine. This project aims to upgrade and test an existing roll-to-roll electrospinner that is more economical for industrial nanofiber production. Varying the diameter of nanofiber can change its functional properties. The current unit cannot adjust spinneret-collector separation, which determines nanofiber diameter. The electro-spinneret channel also does not have lateral adjustment capabilities for precise alignment. Lastly, the viscosities of our polymer solutions have not been quantified. Solution injection into the channel is presently inconsistent because of imperfect nozzle sizing, resulting in waste and decreased efficiency. Modeling was done with Siemens NX CAD software, and viscosity was measured using a Brookfield DVE-LV viscometer. A dual scissor lift design for channel displacement, powered by a dual-shaft DC motor coupled to precision lead screws, was approved and construction was started. Preliminary channel modifications also were initiated. Going forward, the scissor lift system will be integrated and evaluated with our electrospinner, along with further channel modifications. Viscosity measurements of polyvinyldimethylformamide (PVDF) were recorded with inconsistent results due to inadequate testing conditions. Future viscosity trials must be completed in accordance with testing requirements. The optimization and commercialization of roll-to-roll electrospinner units can make nanofiber production more feasible for many new industries and consumer products.
Black, Niko↗
Polymer grafted aramid nanofiber reinforces immiscible waste polypropylene/poly(ethylene terephthalate)
Polypropylene (PP) and poly(ethylene terephthalate) (PET) are plastics commonly used for packaging because of their excellent barrier and mechanical properties. The properties of these plastics are often diminished after mechanical recycling, inevitably causing down-cycling. Furthermore, this problem is exacerbated when different kinds of polymers mix. Aramid nanofibers have the potential to improve the mechanical properties of polymers due to their excellent mechanical properties but their poor dispersion in polymers is a challenge. Grafting polymers onto nanofibers can help address this challenge. In this work, different loading levels (1%, 2%, and 5%) of polymer grafted aramid nanofibers (ANFs) are blended with waste PP/PET (90/10), simulating a PP waste stream containing traces of PET contaminants. Scanning electronic microscopy, rheology, and differential scanning calorimetry results show the affinity of PP functionalized aramid nanofibers (PP_ANF) towards the PP matrix. At 1 wt% of the nanofiber, the size of the PET droplets in the PP matrix of the PP_ANF blend range from 0.2 to 2.0 μm while that of unmodified ANF and PET_ANF blends are in the range of 0.1–6.2 and 0.5–7.4 μm, respectively. In summary, polymer grafted ANFs have the tendency of improving properties of its like polymers due to similarity in the grafting polymer and the polymer matrix.
36 MATERIALS SCIENCE↗
Multifunctional Nanofiber Reinforcement for Improved Thermomechanical and Chemical Stability of Perovskite Solar Cells
This project focused on the development of metal halide perovskite-polymeric nanofiber nanocomposites for robust and efficient solar cells. Metal halide perovskite solar cells are a potentially disruptive technology with high efficiencies and low-cost solution processability amenable with roll-to-roll fabrication of flexible devices. However, perovskites exhibit extreme brittleness, high internal film stresses, and chemical instabilities that significantly limit service lifetimes under normal operating conditions. To date, most work addressing these shortcomings has been focused on encapsulating devices between thick layers of rigid materials such as glass, which increases the total weight and cost of devices. Furthermore, these rigid and heavy encapsulants do not translate well to emerging solar markets vital for national security, including integrated mobile power, emergency deployments for disaster relief and military engagement, and lightweight power for space. It is therefore critical to improve the thermomechanical and chemical stability of perovskite devices in a way that is compatible with flexible and lightweight substrates. In this project, we integrated nylon-6,6 nanofibers into MAPbI3 to mechanically reinforce the perovskite, demonstrating films that exhibited fracture energies 5-fold greater than pristine MAPbI3 while also maintaining similar power conversion efficiencies due to beneficial light scattering effects from the polymeric nanofibers. These results required successful development of approaches to control the deposition thickness of nanofiber mats down to 100s of nanometers, and to ensure the polymer nanofibers did not inhibit charge transport to the at the perovskite-transport layer interface.
14 SOLAR ENERGY↗
Carbon nanofibers based carbon–carbon composite fibers
Textile grade polyacrylonitrile (PAN) was used as a precursor material for carbon fiber preparation. E-beam irradiated polyacrylonitrile grafted carbon nanofibers were dispersed in polyacrylonitrile solution (dissolved in dimethyl formamide). Carbon nanofibers (CNF) infused polyacrylonitrile solution was wet spun on a lab-scale wet-spinning setup to form 50 to 70 µm diameter fibers with 3.2 wt.% CNF-PAN, 6.4 wt.% CNF-PAN, and neat PAN. Precursor fibers were characterized for thermal, mechanical and morphological properties using various techniques. Drawing the precursor fibers further enhanced polymer chain orientation and coalesced the voids, enhancing tensile strength and modulus by more than 150% compared to those of the undrawn fibers. Precursor composite fibers on carbonization showed enhanced strength, compared to that of pristine PAN fibers, by four times and stiffness by 14 times. The carbon–carbon composite fibers were further characterized with SEM/FIB, XRD and tensile strength. The property improvements were dependent on the uniform distribution of carbon nanofibers, and surface modification of carbon nanofibers further enabled their dispersion in the composite fibers. Furthermore, 3.2 wt.% CNFs in PAN fibers showed maximum improvement in properties compared to 6.4 wt.% CNF in PAN fibers, indicating that the property enhancements go through a maximum and then drop off due to challenge in getting uniform distribution of nanofibers.
36 MATERIALS SCIENCE↗
Fabrication and Performance Characterization of Electrospun Nanofibers for Terrestrial and Space Applications
Passive thermal control is vital in space, especially for extended missions involving cryogen storage needing protection from sunlight. This presentation covers the development of a thermal coating with wavelength-selective characteristics using polymeric materials that scatter sunlight with minimal absorption, resulting in high solar reflectance. Furthermore, these coatings allow emission in infrared wavelengths, making them suitable for deep-space missions requiring extended storage. The study chose polymer and surface morphology suitable as solar reflectors that are lightweight, compact, and easily manufacturable, focusing on different multilayered nanofibers made using polytetrafluoroethylene and polyethylene-oxide (PTFE-PEO), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and silica (SiO2). To understand how these materials interact with sunlight, we analyze light propagation through several layers of electrospun nanofibers to determine spectral reflectance, absorptance, and transmittance by solving the Maxwell equations. The model is also compared with measurements of spectral reflectance and transmittance of the various electrospun nanofibers using spectrophotometers interfaced with integrating spheres in the ultraviolet, visible, near-infrared, and mid-infrared wavelengths. The presentation will also describe the design and analysis, fabrication of the nanofibers using electrospinning, and several experimental characterization techniques to determine suitability for space applications. The nanofibers are tested using various tools to determine their suitability for cryogenic applications in space. Lastly, the samples were tested under low vacuum conditions and exposing them to sunlight inside a vacuum chamber maintained at 300 K. Relative to the incoming solar flux (1000 W/m2), only 1% of the energy was absorbed under these operating conditions. With further optimization and testing under high vacuum cryogenic environments, the samples could demonstrate much lower absorption or higher reflection of incoming solar radiation, which can translate to low temperatures suitable for cryogen storage.
Chieloka Ibekwe↗
Structure and dynamics of ILs-based gel polymer electrolytes and its enhanced conductive properties with the incorporation of Al 2 O 3 nanofibers
Here, this work reports the enhanced mobility of ions in ionic liquid (IL)-based gel polymer electrolytes (GPEs) with the incorporation of Al 2 O 3 nanofibers. A combination of PVDF-HFP, EMIMTFSI and LiTFSI with 3 wt% Al 2 O 3 nanofibers has been prepared through solution casting technique. The room temperature ionic conductivity of PVDF-HFP: ILs electrolyte (45:55, weight ratio of 0.82) (GPE) is found to be 2.7 × 10 –5 S cm –1 , which increases up to 7.8 × 10 –5 S cm –1 in Al 2 O 3 containing GPE (Al-GPE). Pulsed field gradient (PFG) NMR results validate the increased ionic conductivity observed in Al-GPE. We found that the diffusivity of Li + , TFSI – and EMIM + increases when Al 2 O 3 nanofibers are well-distributed in the GPE matrix. The surface morphology and the amorphicity of GPEs are examined through SEM and XRD analyses. Lastly, the local structure of Al 2 O 3 fibers and the molecular-level interactions of ions with polymer, and their effect on the diffusivity of ions are established through solid-state NMR detecting 27 Al, 1 H, 13 C, 19 F nuclei including 2D 13 C{ 1 H} HETCOR NMR experiments. The 13 C DPMAS and CPMAS experiments highlight the dynamic heterogeneity associated with the ions that are embedded in the rigid and the mobile phase of GPEs. While some of the ionic species strongly interact with polymer chains in the rigid environment, the majority of them reside in the mobile phase and contribute to the overall increased conductivity. Most importantly, Al 2 O 3 nanofibers significantly affect the dynamics of ionic species that are present in the mobile phase between the polymer chains.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sequence-dependent self-assembly of supramolecular nanofibers in periodic dynamic block copolymers
Block copolymers (BCPs) can spontaneously self-assemble into various nanostructured morphologies which enable their diverse applications in selective membranes, polymer electrolytes, and optoelectronics. To expand the range of nanostructures accessible to block copolymers, we designed dynamic block copolymers (DBCPs) that combine the phase separation of traditional block copolymers with the supramolecular self-assembly of periodic dynamic polymers. We demonstrate that DBCPs synthesized with a periodic block sequence self-assemble into high aspect ratio supramolecular nanofibers with well-ordered PEG and PDMS domains, in contrast to those synthesized with a random sequence which do not form nanofibers but have disordered morphologies. The periodicity of the block sequence ensures regular placement of dynamic bonds along the polymer chain, which enables stacking of the hydrogen bonding units into ordered 1D supramolecular nanofibers and delays the onset of terminal flow by up to 60 °C compared to the random block sequence. The hierarchically assembled supramolecular nanofibers display complex mechanical and thermal phase behavior arising from the interplay between phase separation of the dissimilar polymer backbones and supramolecular interactions between dynamic bonds. Despite identical bulk composition, the periodic DBCPs demonstrate ionic conductivity values over two orders of magnitude higher than their random counterparts due to the formation of well-ordered, interconnected, high aspect ratio ion-transporting PEG domains. In conclusion, these results highlight the potential for DBCPs as an emerging material platform to achieve advanced, self-assembled nanostructured morphologies.
36 MATERIALS SCIENCE↗
Compact scalable nanofiber mass production using electrospinning
A low power out put high voltage power supply unit for mass producing thicker nanofiber mat has been built in-house and earned a provisional patent last year. This nanofiber fabrication unit has unique features to produce stand alone thick ceramic nanofiber for specialized application such as isotop production and accelerator targets for high energy physics experiments. This is a versatile unit which can produce wide variety of polymer nanofibers on a semi industrial scale for application in air filtration, face mask, facial beauty pads, gas sensors and many more.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Electrical Characterization of Polyaniline/polyethylene Oxide Nanofibers for Field Effect Transistors
Nanofibers comprised of polyaniline/polyethylene oxide (PANI/PEO) are being developed for novel logic devices. We report the electrical conductivity of PANI/PEO nanofibers with diameters in the 100 to 200 nm range. We measured conductivity values of approx. 0.3 to 1.0 S/cm, which is higher than the values reported for thicker nanofibers, but less than the bulk value of PANI. The electrical measurements were performed by depositing the fibers on pre-electroded, oxidized silicon (Si) substrates. The excellent adherence of the nanofibers to the SiO2 as well as the gold (Au) electrodes may be useful in the design of future devices.
Mueller, Carl H.↗
Electrospun Nanofiber Coating of Fiber Materials: A Composite Toughening Approach
Textile-based composites could significantly benefit from local toughening using nanofiber coatings. Nanofibers, thermoplastic or otherwise, can be applied to the surface of the fiber tow bundle, achieving toughening of the fiber tow contact surfaces, resulting in tougher and more damage-resistant/tolerant composite structures. The same technique could also be applied to other technologies such as tape laying, fiber placement, or filament winding operations. Other modifications to the composite properties such as thermal and electrical conductivity could be made through selection of appropriate nanofiber material. Control of the needle electric potential, precursor solution, ambient temperature, ambient humidity, airflow, etc., are used to vary the diameter and nanofiber coating morphology as needed. This method produces a product with a toughening agent applied to the fiber tow or other continuous composite precursor material where it is needed (at interfaces and boundaries) without interfering with other composite processing characteristics.
Kohlman, Lee W.↗
Electrospun Nanofibers
Electrospun nanofibers have been considered promising separator candidates for lithium–sulfur (Li–S) batteries due to their unique properties, including but not limited to their high surface area, superior surface-to-volume ratio, excellent flexibility, good mechanical performance, etc. This chapter aims to provide an overview of research in electrospun nanofibers with their applications in Li–S batteries. It starts with a brief introduction to Li–S batteries, followed by the principle and advantages of electrospun nanofibers performed in this area. Applications of electrospun separators in Li–S batteries have been further discussed in detail. In the end, a future vision regarding challenges and perspectives is proposed to provide insightful comments in this field. It is believed that this chapter will provide an extensive and comprehensive reference to utilize this advanced technique to generate novel nanofiber separators for next-generation Li–S batteries.
Zhu, Jiadeng↗
Hybrid Bio-Based Composites: Enabling Cellulose Nanofiber (CNF) Incorporation into Composites via Macroscale Natural Fiber Carriers
Cellulose nanofibers (CNFs) have significant potential in composites as additives to improve mechanical properties, melt rheology, and more. However, agglomeration of CNFs is a key challenge in composite melt processing as obtaining nano-level dispersion of CNFs often requires cost- and energy-intensive processes (e.g., solvent exchange or freeze drying) due to the strong hornification tendencies of CNF. Herein, we avoid these challenges by using a natural fiber carrier method to integrate CNF into thermoplastic composites. Fibers are co-dried to create a hybrid fiber feedstock for compounding in which natural fibers are decorated with dispersed nanofibers. The hybridized fibers result in up to a 24% increase in tensile strength and up to a 35% increase in Young’s modulus compared to composites only containing natural fibers. The lignocellulosic nanofibers are found to outperform their purely cellulosic counterpart, which is theorized to be due to either an increased propensity for fibrillation of the lignocellulosic fibers or the increased hydrophobicity of the fibers due to the presence of lignin. Surface analysis of fiber feedstocks, via streaming potential measurements and dynamic light scattering (DLS), confirmed a significant change in the feedstock hydrophobicity before and after hybridization. While mild additions of CNF (1 wt.% on the macroscale fiber) do not impact the composite melt viscosity, the viscosity is found to increase at higher CNF loadings (5 wt.% on the macroscale fiber), indicating its utility as a rheology modifier. Lastly, use of these materials as novel feedstocks for medium-scale additive manufacturing in high-fidelity part production was demonstrated.
bio-based↗
Self‐Standing Carbon Nanofibers@Carbon Felt Electrodes to Boost Electrolyzer Productivity: Application to the Electro‐Manufacturing of trans ‐3‐Hexenedioic Acid and Adipic Acid
The industrial implementation of electrosynthesis for chemical manufacturing remains constrained by the limited surface area of conventional electrodes. Herein, this challenge is addressed by designing a carbon nanofiber@carbon felt (CNF@CF) electrode platform that combines the high conductivity, flexibility, and ease of handling of commercial carbon felts (CF) with the large surface area and tunable surface chemistry of carbon nanofibers (CNFs). CNFs are deliberately grown onto the CF scaffold to form a sword-in-sheath structure, where entangled nanofibers wrap the felt macrofibers to provide excellent mechanical stability and electrical conductivity without binders. CNF@CF is evaluated both as an electrode and as a catalyst support for the electrochemical hydrogenation of cis,cis-muconic acid (ccMA), a biobased platform molecule key to the production of performance polyamides and renewable Nylon 6,6. As a noncatalytic electrode for the partial hydrogenation to trans-3-hexenedioic acid, CNF@CF achieves a threefold increase in both cumulative productivity and Faradaic efficiency (FE) compared to bare CF. A similar boost in catalytic activity and energy efficiency is observed using Pd/CNF@CF for the hydrogenation of ccMA to adipic acid. These results highlight the opportunities of the CNF@CF platform for electro-organic synthesis and sustainable chemical manufacturing.
electrochemical hydrogenation↗