Margaret W. Frey

Electrospinning Cellulose and Cellulose Derivatives

Many solvents suitable for wet or dry spinning of cellulose and cellulose derivatives have also been investigated as solvents for electrospinning. Solvents for cellulose are not completely volatile and have required coagulation steps to ensure complete removal of the solvent from electrospun fibers and produce stable fibers. Cellulose derivatives include cellulose acetate, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and ethyl‐cyanoethyl cellulose, which can be dissolved in volatile solvents suitable for electrospinning. Cellulose acetate in particular has been electrospun under a wide variety of conditions and subsequently deacetylated to form cellulose nanofibers or functionalized with other side groups.

Characterizing zeta potential of functional nanofibers in a microfluidic device.

The measurement of surface charge on nanofibers was achieved by characterizing zeta potential of the nanofibers via a newly developed device for streaming current measurement. Low flow rates were sufficient to generate detectable streaming currents in the absence of an externally applied voltage without damaging nanofiber samples. Zeta potential was calculated by using the Helmholtz-Smoluchowski equation and the measured streaming currents. Two acrylic plates were machined and assembled to form a microfluidic channel that is 150 μm high, 2.0mm wide, and 30 mm long. Two electrodes for the measurement of streaming currents were housed in the top plate. Two nanofibers of pure polyacrylonitrile (PAN) fibers and charged (TiO(2) incorporated) PAN fibers were prepared and characterized in the device. Monobasic sodium phosphate and dibasic sodium phosphate were used to prepare four different pH buffer solutions ranging from pH 5 to pH 8 in order to characterize the zeta potentials. The pure PAN nanofibers had negatively-charged surfaces regardless of pH. However, the zeta potentials of PAN/TiO(2) nanofibers changed from positive to negative at pH 6.5. The zeta potential measurements made on the nanofibers in this new microfluidic device matched with those of the powdered raw materials using a commercial Zetasizer.

Preparation and Characterization of Amphiphilic Triblock Terpolymer-Based Nanofibers as Antifouling Biomaterials

Antifouling surfaces are critical for the good performance of functional materials in various applications including water filtration, medical implants, and biosensors. In this study, we synthesized amphiphilic triblock terpolymers (tri-BCPs, coded as KB) and fabricated amphiphilic nanofibers by electrospinning of solutions prepared by mixing the KB with poly(lactic acid) (PLA) polymer. The resulting fibers with amphiphilic polymer groups exhibited superior antifouling performance to the fibers without such groups. The adsorption of bovine serum albumin (BSA) on the amphiphilic fibers was about 10-fold less than that on the control surfaces from PLA and PET fibers. With the increase of the KB content in the amphiphilic fibers, the resistance to adsorption of BSA was increased. BSA was released more easily from the surface of the amphiphilic fibers than from the surface of hydrophobic PLA or PET fibers. We have also investigated the structural conformation of KB in fibers before and after annealing by contact angle measurements, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and coarse-grained molecular dynamics (CGMD) simulation to probe the effect of amphiphilic chain conformation on antifouling. The results reveal that the amphiphilic KB was evenly distributed within as-spun hybrid fibers, while migrated toward the core from the fiber surface during thermal treatment, leading to the reduction in antifouling. This suggests that the antifouling effect of the amphiphilic fibers is greatly influenced by the arrangement of amphiphilic groups in the fibers.

Morphological characteristics of the lyotropic and gel phases in the cellulose/NH3/NH4SCN system

Solutions of cellulose in the ammonia/ammonium thiocyanate (24.5/75.5 w/w) solvent form several stable phases. Of particular interest in this work are the temperature-dependent liquid crystalline and gel phases which are stable at cellulose concentrations above 6% w/v. While the temperature-composition conditions yielding these phases are reasonably well established, very little is currently known about the morphological characteristics of lyotropic and gelled cellulose. Polarized light microscopy is employed here to demonstrate that solutions at temperatures above the gel melting point are birefringent, composed of liquid crystals. Field-emission scanning electron microscopy has been used to (i) examine the three-dimensional network in cellulose gels, and (ii) correlate network morphology with cellulose molecular weight and solution concentration. Results obtained from two complementary sample preparation techniques (i.e., critical point drying and freeze drying) are compared to identify and minimize artifacts, and reveal that gel formation occurs as the solutions phase-separate into polymer-rich anisotropic and solvent-rich isotropic phases. The polymer-rich phase is highly interconnected and forms a fibrillar network, with fibrils measuring 20-70 nm in diameter.

Increasing Mechanical Properties of 2-D-Structured Electrospun Nylon 6 Non-Woven Fiber Mats

Tensile strength, Young’s modulus, and toughness of electrospun nylon 6 non-woven fiber mats were improved by increasing individual nanofiber strength and fiber–fiber load sharing. Single-walled carbon nanotubes (CNTs) were used as reinforcement to increase the strength of the electrospun nylon 6 nanofibers. Young’s modulus, tensile strength, and toughness of the nylon 6 non-woven fiber mats electrospun from 20 wt % solutions increased 51%, 87%, and 136%, respectively, after incorporating 1 wt % CNTs into the nylon 6 nanofibers. Three methods were investigated to enhance fiber–fiber load sharing: increasing friction between fibers, thermal bonding, and solvent bonding. The addition of beaded nylon 6 nanofibers into the non-woven fiber mats to increase fiber-fiber friction resulted in a statistically significantly increase in Young’s modulus over comparable smooth non-woven fiber mats. After annealing, tensile strength, elongation, and toughness of the nylon 6 non-woven fiber mats electrospun from 20 wt % + 10 wt % solutions increased 26%, 28%, and 68% compared to those from 20 wt % solutions. Solvent bonding with formic acid vapor at room temperature for 30 min caused increases of 56%, 67%, and 39% in the Young’s modulus, tensile strength, and toughness of non-woven fiber mats, respectively. The increases attributed to increased individual nanofiber strength and solvent bonding synergistically resulted in the improvement of Young’s modulus of the electrospun nylon 6 non-woven fiber mats.

Surface Functional Poly(lactic Acid) Electrospun Nanofibers for Biosensor Applications

In this work, biotin surface functionalized hydrophilic non-water-soluble biocompatible poly(lactic acid) (PLA) nanofibers are created for their potential use as biosensors. Varying concentrations of biotin (up to 18 weight total percent (wt %)) were incorporated into PLA fibers together with poly(lactic acid)-block-poly(ethylene glycol) (PLA-b-PEG) block polymers. While biotin provided surface functionalization, PLA-b-PEG provided hydrophilicity to the final fibers. Morphology and surface-available biotin of the final fibers were studied by Field Emission Scanning Electron Microscopy (FESEM) and competitive colorimetric assays. The incorporation of PLA-b-PEG block copolymers not only decreased fiber diameters but also dramatically increased the amount of biotin available at the fiber surface able to bind avidin. Finally, fiber water stability tests revealed that both biotin and PLA-b-PEG, migrated to the aqueous phase after relatively extended periods of water exposure. The functional hydrophilic nanofiber created in this work shows a potential application as a biosensor for point-of-care diagnostics.

Passive Mixing Capabilities of Micro- and Nanofibres When Used in Microfluidic Systems

Nanofibres are increasingly being used in the field of bioanalytics due to their large surface-area-to-volume ratios and easy-to-functionalize surfaces. To date, nanofibres have been studied as effective filters, concentrators, and immobilization matrices within microfluidic devices. In addition, they are frequently used as optical and electrochemical transduction materials. In this work, we demonstrate that electrospun nanofibre mats cause appreciable passive mixing and therefore provide dual functionality when incorporated within microfluidic systems. Specifically, electrospun nanofibre mats were integrated into Y-shaped poly(methyl methacrylate) microchannels and the degree of mixing was quantified using fluorescence microscopy and ImageJ analysis. The degree of mixing afforded in relationship to fibre diameter, mat height, and mat length was studied. We observed that the most mixing was caused by small diameter PVA nanofibres (450–550 nm in diameter), producing up to 71% mixing at the microchannel outlet, compared to up to 51% with polystyrene microfibres (0.8–2.7 μm in diameter) and 29% mixing in control channels containing no fibres. The mixing afforded by the PVA nanofibres is caused by significant inhomogeneity in pore size and distribution leading to percolation. As expected, within all the studies, fluid mixing increased with fibre mat height, which corresponds to the vertical space of the microchannel occupied by the fibre mats. Doubling the height of the fibre mat led to an average increase in mixing of 14% for the PVA nanofibres and 8% for the PS microfibres. Overall, mixing was independent of the length of the fibre mat used (3–10 mm), suggesting that most mixing occurs as fluid enters and exits the fibre mat. The mixing effects observed within the fibre mats were comparable to or better than many passive mixers reported in literature. Since the nanofibre mats can be further functionalized to couple analyte concentration, immobilization, and detection with enhanced fluid mixing, they are a promising nanomaterial providing dual-functionality within lab-on-a-chip devices.

Piezoelectric Poly(3-hydroxybutyrate)-Poly(lactic acid) Three Dimensional Scaffolds for Bone Tissue Engineering

Three dimensional scaffolds (3D) are promising for future nanoscale materials and tissue engineering applications being that they have architecture and mechanical properties similar to natural tissue. In this work, poly(lactic acid) fibers were prepared via electrospinnig with average diameters of 2580 nm. Using Enzymatic Surface-Initiated polymerization (ESIP), poly(3-hydroxybutyrate) were coated on poly(lactic acid) fibers. This provides an alternative method to enzymatic surface modification of fibers. ESIP of PHB produces a granular film providing surface topography and increases mechanical properties of PLA fibers alone. When using covalent approaches, PHB granules provide surface topography of 200-500 nm with a polydisperse coverage area. Compressive modulus measurements of PLA and PHB/PLA scaffolds were 25 kPa and 73 kPa, respectively. The percent crystallinity of PLA and PHB/PLA scaffolds was 17% and 30%, respectively. This rough topography, in addition to the crystallinity of the scaffold, facilitates Soas-2 osteoblast cell attachment. We have observed attachment of the osteoblast cells along the length of the oriented PLA and PHB/PLA composite scaffolds with different morphologies, rounded and stretched, throughout a depth of 90 µm.

Developing composite nanofibre fabrics using electrospinning, ultrasonic sewing, and laser cutting technologies

ABSTRACT In this study, we combine Nylon 6 nanomembranes with tulle and organza fashion fabrics to construct a full-scale, flying kite. For the first time, this work demonstrates the processing of electrospun nanofabrics using laser cut and ultrasonic technologies. The composite fabrics were analysed for their morphological and mechanical properties. Micrographs show the nanofibres are about 129 nm in diameter and the fashion fabrics have yarn diameters greater than 40 µm. The nanofibres were at least 300 times smaller than the individual fibres in the fashion fabrics and successfully joined with non-puncturing ultrasonic seaming. The fracture strain of the nanomembrane–tulle composites increased 58–171% compared to the control samples due to nanofibre entanglements on the open weave structure of tulle. The ultrasonic sewn fabric regions endured 169% greater applied stress with the addition of the organza fabric and the seaming process compared to the nanomembrane–tulle composite. The burst strength of the composites compared to the controls did not change. The integration of these technologies allows us to manufacture nanofibres with everday textiles to fit many potential applications and uses. The provided supplementary video shows the assembly process and flying of the kite as proof-of-concept.

Formation and functions of high-surface-area fabrics

Non-woven fabrics made from fibres with submicron diameters have extremely high surface-to-volume ratios, which can be tailored and used in a variety of applications. In our research laboratories, fabrics have been made by the electrospinning process. The fabrication method can be adjusted to control the pore spacing between fabrics by controlling the density of fibre collection. By combining dissimilar materials including cellulose nanocrystals, nanoclay and biotin within the nano fibres, we have been able to adjust the strength and the surface properties of the fabrics. Fabrics have been created that can selectively capture biohazards from liquids and particles or volatile organic compounds from air.