Many commodity plastics, such as thermoplastic polyurethanes (PUs), require reinforcement for use as commercial products. Cellulose nanocrystals (CNCs) offer a “green” and scalable approach to polymer reinforcement as they are exceptionally stiff, recyclable, and abundant. Unfortunately, achieving efficient CNC reinforcement of PUs with industrial melt processing techniques is difficult, mostly due to the incompatibility of the hydrophobic PU with hydrophilic CNCs, limiting their dispersion. Here, a hydrophilic PU is synthesized to achieve strong reinforcement in melt‐processed nanocomposite fibers using filter paper‐sourced CNCs. The melt‐spun fibers, exhibiting smooth surfaces even at high CNC loading (up to 25 wt%) indicating good CNC dispersion, are bench‐marked against solvent‐cast films—solvent processing is not scalable but disperses CNCs well and produces strong CNC reinforcement. Mechanical analysis shows the CNC addition stiffens both nanocomposite films and fibers. The stress and strain at break, however, are not significantly affected in films, whereas adding CNCs to fibers increases the stress‐at‐break while reducing the strain‐at‐break. Compared to earlier studies employing a hydrophobic (and stiffer) PU, CNC addition to a hydrophilic PU substantially increases the fiber stiffness and strength. This work therefore suggests that rendering thermoplastics more hydrophilic might pave the way for “greener” polymer composite products using CNCs.
- Award ID(s):
- 1844463
- PAR ID:
- 10167143
- Date Published:
- Journal Name:
- Polymers
- Volume:
- 12
- Issue:
- 5
- ISSN:
- 2073-4360
- Page Range / eLocation ID:
- 1021
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
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
-
The fabrication of nanocomposite films and fibers based on cellulose nanocrystals (P-tCNCs) and a thermoplastic polyurethane (PU) elastomer is reported. High-aspect-ratio P-tCNCs were isolated from tunicates using phosphoric acid hydrolysis, which is a process that affords nanocrystals displaying high thermal stability. Nanocomposites were produced by solvent casting (films) or melt-mixing in a twin-screw extruder and subsequent melt-spinning (fibers). The processing protocols were found to affect the orientation of both PU hard segments and the P-tCNCs within the PU matrix and therefore the mechanical properties. While the films were isotropic, both the polymer matrix and the P-tCNCs proved to be aligned along the fiber direction in the fibers, as shown using SAXS/WAXS, angle-dependent Raman spectroscopy, and birefringence analysis. Tensile tests reveal that fibers and films, at similar P-tCNC contents, display Young’s moduli and strain-at-break that are within the same order of magnitude, but the stress-at-break was found to be ten-times higher for fibers, conferring them a superior toughness over films.more » « less
-
more » « less
Natural white silk cocoons exhibit strong broadband optical scattering by Anderson localization within the silk fibers, providing a low‐light environment to the pupae inside. This scattering effect is due to thousands of densely packed parallel fibrillar nanovoids running within each fiber along the fiber axis. Herein, to enhance sunlight rejection from white silk, conventional diffusive optical transport without Anderson localization is used. For optical diffusion, natural white silk is restructured by electrospinning to destroy the fibrillar nanovoids. Sunlight rejection power of the electrospun structures is controlled by the fiber diameters. Relative to a nonwoven raw silk fabric, a restructured silk film with a mean fiber diameter of a quarter micron substantially increases optical scattering strength in the visible spectrum and emissivity in the mid‐infrared atmospheric transparency window. The restructured silk fibrous film can reduce the average temperature of a substrate, on which the film is coated, by 7.5 °C relative to a nonwoven raw silk fabric during daytime under solar radiation. The results suggest that artificially processed polymeric fiber mats can achieve substantially stronger sunlight rejection than natural silk, by using optical diffusion without Anderson localization. These polymeric mats are useful as sunshades in various applications.
-
more » « less
In this work, electrospun polyvinylidene-trifluoroethylene (PVDF-TrFE) was utilized for its biocompatibility, mechanics, and piezoelectric properties to promote Schwann cell (SC) elongation and sensory neuron (SN) extension. PVDF-TrFE electrospun scaffolds were characterized over a variety of electrospinning parameters (1, 2, and 3 h aligned and unaligned electrospun fibers) to determine ideal thickness, porosity, and tensile strength for use as an engineered skin tissue. PVDF-TrFE was electrically activated through mechanical deformation using low-intensity pulsed ultrasound (LIPUS) waves as a non-invasive means to trigger piezoelectric properties of the scaffold and deliver electric potential to cells. Using this therapeutic modality, neurite integration in tissue-engineered skin substitutes (TESSs) was quantified including neurite alignment, elongation, and vertical perforation into PVDF-TrFE scaffolds. Results show LIPUS stimulation promoted cell alignment on aligned scaffolds. Further, stimulation significantly increased SC elongation and SN extension separately and in coculture on aligned scaffolds but significantly decreased elongation and extension on unaligned scaffolds. This was also seen in cell perforation depth analysis into scaffolds which indicated LIPUS enhanced perforation of SCs, SNs, and cocultures on scaffolds. Taken together, this work demonstrates the immense potential for non-invasive electric stimulation of an in vitro tissue-engineered-skin model.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/polym12051021
