This paper reports the molecular organization and mechanical properties of electrospun, post-drawn polyacrylonitrile (PAN) nanofibers. Without post-drawing, the polymer chain was kinked and oriented in hexagonal crystalline structures. Immediate post-drawing in the semi-solid state disrupted the crystal structures and chain kink at maximum draw ratio. Structural re-orientation at maximum draw resulted in a 500% increase in Young's modulus and a 100% increase in ultimate tensile strength. By applying post-drawing to electrospinning it may be possible to obtain PAN fibers and PAN-derived carbon fibers with enhanced mechanical properties compared to available fabrication technologies.
more »
« less
Well-Adhered Copper Nanocubes on Electrospun Polymeric Fibers
Electrospun polymer fibers can be used as templates for the stabilization of metallic nanostructures, but metallic species and polymer macromolecules generally exhibit weak interfacial adhesion. We have investigated the adhesion of model copper nanocubes on chemically treated aligned electrospun polyacrylonitrile (PAN) fibers based on the introduction of interfacial shear strains through mechanical deformation. The composite structures were subjected to distinct macroscopic tensile strain levels of 7%, 11%, and 14%. The fibers exhibited peculiar deformation behaviors that underscored their disparate strain transfer mechanisms depending on fiber size; nanofibers exhibited multiple necking phenomena, while microfiber deformation proceeded through localized dilatation that resulted in craze (and microcrack) formation. The copper nanocubes exhibited strong adhesion on both fibrous structures at all strain levels tested. Raman spectroscopy suggests chemisorption as the main adhesion mechanism. The interfacial adhesion energy of Cu on these treated PAN nanofibers was estimated using the Gibbs–Wulff–Kaischew shape theory giving a first order approximation of about 1 J/m2. A lower bound for the system’s adhesion strength, based on limited measurements of interfacial separation between PAN and Cu using mechanically applied strain, is 0.48 J/m2.
more »
« less
- Award ID(s):
- 1634772
- PAR ID:
- 10342709
- Date Published:
- Journal Name:
- Nanomaterials
- Volume:
- 10
- Issue:
- 10
- ISSN:
- 2079-4991
- Page Range / eLocation ID:
- 1982
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
We present a study of the mechanical behavior of planar fibrous mats stabilized by inter-fiber adhesion. Fibers of various degrees of tortuosity and of infinite and finite length are considered in separate models. Fibers are randomly distributed, are not cross-linked, and interact through adhesion and friction. The variation of structural parameters such as the mat thickness and the mean segment length between contacts along given fibers with the strength of adhesion is determined. These systems are largely dissipative in that most of the work performed during deformation is dissipated frictionally and only a small fraction is stored as strain energy. The response of the mats to tensile loading has three regimes: a short elastic regime in which no sliding at contacts is observed, a well-defined sliding regime characterized by strain hardening, and a rapid stiffening regime at larger strains. The third regime is due to the formation of stress paths after the fiber tortuosity is pulled out and is absent in mats of finite length fibers. Networks of finite length fibers lose stability during the second regime of deformation. The scaling of the yield stress, which characterizes the transition between the first and the second regimes, and of the second regime's strain hardening modulus, with system parameters such as the strength of adhesion and friction and the degree of fiber tortuosity are determined. The strength of mats of finite length fibers is also determined as a function of network parameters. These results are expected to become useful in the design of electrospun mats and other planar fibrous non-cross-linked networks.more » « less
-
null (Ed.)In this study, hexagonal boron nitride (h-BN) nanosheets and Bombyx mori silk fibroin (SF) proteins were combined and electrospun into BNSF nanofibers with different ratios. It was found that the surface morphology and crosslinking density of the nanofibers can be tuned through the mixing ratios. Fourier transform infrared spectroscopy study showed that pure SF electrospun fibers were dominated by random coils and they gradually became α-helical structures with increasing h-BN nanosheet content, which indicates that the structure of the nanofiber material is tunable. Thermal stability of electrospun BNSF nanofibers were largely improved by the good thermal stability of BN, and the strong interactions between BN and SF molecules were revealed by temperature modulated differential scanning calorimetry (TMDSC). With the addition of BN, the boundary water content also decreased, which may be due to the high hydrophobicity of BN. These results indicate that silk-based BN composite nanofibers can be potentially used in biomedical fields or green environmental research.more » « less
-
Co-axial electrospinning is an efficient technique to develop core-shell or hollow nanofibrous structures. In this study electrospun carbon nanofibers with three different morphologies, i.e. solid nanofibers with porous structure (P-ECNF), hollow nanofibers with solid wall (H-ECNF), and hollow nanofibers with porous wall (HP-ECNF) were developed through bicomponent electrospinning and co-axial electrospinning of polyacrylonitrile (PAN) and poly (methyl methacrylate) (PMMA) by varying proportion of the sacrificial PMMA. Through comparative electrochemical analyses, it is revealed that the primary factors for electrochemical performance, i.e. specific capacitance, of the electrospun carbon nanofibrous materials are mesopore volume and total pore volume. The hollow structure as well as ordered carbon structure and intact fiber structure also benefits electrolyte transfer and subsequent electrochemical performance but is secondary. Overall the porous carbon nanofibrous electrode material from electrospinning PAN/PMMA (50/50) solution (P-ECNF-50-50) outperformed those hollow and hollow-porous counterparts from co-axial electrospinning and demonstrated the largest specific capacitance due to the largest mesopore volume as well as the largest total pore volume. This electrode material also showed excellent cycling stability (without any loss of specific capacitance) after 3,000 cycles of charging and discharging. It even showed some increase of specific capacitance with cycling test due to its relatively large amount of micropores.more » « less
-
The addition of plasmonic nanoparticles into electrospun polymer fibers can have significant impact on their properties relevant to applications in sensing, catalyst, and energy conversion. A Raman spectrometer incorporated into a photothermal heterodyne imaging system was used to study the hot electron transfer mechanism generated through excitation of a localized surface plasmon resonance (LSPR) of gold and silver nanoparticles in polyacrylonitrile films and nanofibers. The ratio of anion nitrile radicals to neutral nitriles of polyacrylonitrile, provides a measure of the ionization capabilities of the nanoparticles, was found to follow a Boltzmann distribution, indicating that the LSPR mediated hot electron transfer mechanism is dependent on temperature. Silicon nanoparticles were used as a control for temperature and showed that heating itself, using 405 nm and 532 nm pump lasers, was not sufficient to ionize polyacrylonitriles, even at relatively high temperatures. The results provide insight into the roles of heating and electron transfer arising from nanoparticles additives in electrospun polymer fibers and other materials.more » « less