Urszula Stachewicz

In situ tensile testing of nanofibers by combining atomic force microscopy and scanning electron microscopy

A nanomechanical testing set-up is developed by integrating an atomic force microscope (AFM) for force measurements with a scanning electron microscope (SEM) to provide imaging capabilities. Electrospun nanofibers of polyvinyl alcohol (PVA), nylon-6 and biological mineralized collagen fibrils (MCFs) from antler bone were manipulated and tensile-tested using the AFM-SEM set-up. The complete stress-strain behavior to failure of individual nanofibers was recorded and a diversity of mechanical properties observed, highlighting how this technique is able to elucidate mechanical behavior due to structural composition at nanometer length scales.

Enhanced wetting behavior at electrospun polyamide nanofiber surfaces.

Nanofibers of polyamide have been synthesized using electrospinning processes and their wetting properties determined directly from a nanoscale Wilhelmy balance approach. Individual electrospun polyamide nanofibers were attached to atomic force microscope (AFM) tips and immersed in a range of organic liquids with varying polar and dispersive surface tension components. AFM was used to measure nanofiber-liquid wetting forces and derive contact angles using Wilhelmy balance theory. Owens-Wendt plots were used to show a considerable increase in the polar component of the surface free energy of the polyamide nanofibers compared with bulk film of the same polymer. Chemical surface analysis of the polyamide nanofibers and films using X-ray photoelectron spectroscopy provided evidence for enhanced availability of polar oxygen groups at the electrospun nanofiber surface relative to the film. Our results therefore confirm chemical group orientation at the electrospun polyamide nanofiber surface that promotes availability of polar groups for enhanced wetting behavior.

Relaxation Times in Single Event Electrospraying Controlled by Nozzle Front Surface Modification

Single event electrospraying (SEE) is a method for on-demand deposition of femtoliter to picoliter volumes of fluids. To determine the influence of the size of the meniscus on the characteristics of the single event electrospraying process, glass capillaries were used with and without an antiwetting coating comprising a self-assembled 1H,1H,2H,2H-perfluorodecyltrichlorosilane-based monolayer to control the meniscus size. A large difference was found in driving single event electrospraying from a small meniscus compared to what is needed to generate a single event electrospraying from a large meniscus. Furthermore, after studying the different time constants related to the electrical and the hydrodynamic phenomena, we are able to explain the timing limitations of the deposition process from both a small and a large meniscus. The hydrodynamic relaxation time is significantly reduced in the case of the modified capillary, and the timing of SEE, which determines the deposition time, is limited by the resistor-capacitor RC time of the electrical circuit needed to drive the SEE. We have built a model that describes the almost one-dimensional motion of the liquid in the capillary during pulsing. The model has been used to estimate the hydrodynamic relaxation times related to the meniscus-to-cone and cone-to-meniscus transitions during SEE. By confining the meniscus to the inner diameter of the nozzle, we are able to deposit a volume smaller than 5 pL per SEE.

Manufacture of Void-Free Electrospun Polymer Nanofiber Composites with Optimized Mechanical Properties

Engineered fiber reinforced polymer composites require effective impregnation of polymer matrix within the fibers to form coherent interfaces. In this work, we investigated solution interactions with electrospun fiber mats for the manufacture of nanocomposites with optimized mechanical properties. Void free composites of electrospun nonwoven PA6 nanofibers were manufactured using a PVA matrix that is introduced into the nonwoven mat using a solution-based processing method. The highest failure stress of the composites was reported for an optimum 16 wt % of PVA in solution, indicating the removal of voids in the composite as the PVA solution both impregnates the nanofiber network and fills all the pores of the network with PVA matrix upon evaporation of the solvent. These processing methods are effective for achieving coherent nanofiber-matrix interfaces, with further functionality demonstrated for optically transparent electrospun nanofiber composites.

Stress delocalization in crack tolerant electrospun nanofiber networks.

The fracture toughness of a noncontinuum fibrous network produced by electrospinning polyamide 6 nanofibers is investigated. The mechanical properties of the nanofiber network is observed to be independent of various incorporated macroscopic crack lengths, resulting in an apparent increase in fracture toughness with increasing crack length as evaluated using conventional fracture mechanics. Strain mapping of the nanofiber network indicates stress delocalization mechanisms operating around these macroscopic cracks in the network. The deformation behavior of the nanofiber network will therefore depend on the volume of fibers being loaded in the network and not the number of fibers in the cross-sectional width defining continuum sample mechanics. These results indicate a propensity for both the synthetic electrospun nanofibrous network in this work and potentially other nanofibrous networks to resist failure from macroscopic cracks incorporated within the material.

3D imaging of cell interactions with electrospun PLGA nanofiber membranes for bone regeneration.

UNLABELLED The interaction between resident cells and electrospun nanofibers is critical in determining resultant osteoblast proliferation and activity in orthopedic tissue scaffolds. The use of techniques to evaluate cell-nanofiber interactions is critical in understanding scaffold function, with visualization promising unparalleled access to spatial information on such interactions. 3D tomography exploiting focused ion beam (FIB)-scanning electron microscopy (SEM) was used to examine electrospun nanofiber scaffolds to understand the features responsible for (osteoblast-like MC3T3-E1 and UMR106) cell behavior and resultant scaffold function. 3D imaging of cell-nanofiber interactions within a range of electrospun poly(d,l-lactide-co-glycolide acid) (PLGA) nanofiber scaffold architectures indicated a coherent interface between osteoblasts and nanofiber surfaces, promoting osteoblast filopodia formation for successful cell growth. Coherent cell-nanofiber interfaces were demonstrated throughout a randomly organized and aligned nanofiber network. Gene expression of UMR106 cells grown on PLGA fibers did not deviate significantly from those grown on plastic, suggesting maintenance of phenotype. However, considerably lower expression of Ibsp and Alpl on PLGA fibers might indicate that these cells are still in the proliferative phase compared with a more differentiated cell on plastic. This work demonstrates the synergy between designing electrospun tissue scaffolds and providing comprehensive evaluation through high resolution imaging of resultant 3-dimensional cell growth within the scaffold. STATEMENT OF SIGNIFICANCE Membranes made from electrospun nanofibers are potentially excellent for promoting bone growth for next-generation tissue scaffolds. The effectiveness of an electrospun membrane is shown here using high resolution 3D imaging to visualize the interaction between cells and the nanofibers within the membrane. Nanofibers that are aligned in one direction control cell growth at the surface of the membrane whereas random nanofibers cause cell growth into the membrane. Such observations are important and indicate that lateral cell growth at the membrane surface using aligned nanofibers could be used for rapid tissue repair whereas slower but more extensive tissue production is promoted by membranes containing random nanofibers.

Charge assisted tailoring of chemical functionality at electrospun nanofiber surfaces

Electrospinning using positive and negative polarity applied voltages is used to produce polyamide nanofibers with tailored surface functionality. The surface free energy of the resultant nanofibers is characterized from individual nanofiber wetting experiments. The polar contribution to the total nanofiber surface energy is seen to vary with the polarity of the applied voltage used. A mechanism to describe the change in the nanofiber surface free energy with electrospinning polarity is proposed, based on the formation of either positive or negative charges at the liquid jet–air interface during the electrospinning process. These charges at the liquid jet–air interface cause molecular orientation of chemical functional groups of the polymer chains during electrospinning and the mechanism is supported by subsequent grazing angle X-ray photoelectron spectroscopy (XPS) of the nanofiber surfaces. A one-step electrospinning process is therefore demonstrated to tailor specific chemical functionalities at polymer nanofiber surfaces.

Wetting Hierarchy in Oleophobic 3D Electrospun Nanofiber Networks.

Wetting behavior between electrospun nanofibrous networks and liquids is of critical importance in many applications including filtration and liquid-repellent textiles. The relationship between intrinsic nanofiber properties, including surface characteristics, and extrinsic nanofibrous network organization on resultant wetting characteristics of the nanofiber network is shown in this work. Novel 3D imaging exploiting focused ion beam (FIB) microscopy and cryo-scanning electron microscopy (cryo-SEM) highlights a wetting hierarchy that defines liquid interactions with the network. Specifically, small length scale partial wetting between individual electrospun nanofibers and low surface tension liquids, measured both using direct SEM visualization and a nano Wilhelmy balance approach, provides oleophobic surfaces due to the high porosity of electrospun nanofiber networks. These observations conform to a metastable Cassie-Baxter regime and are important in defining general rules for understanding the wetting behavior between fibrous solids and low surface tension liquids for omniphobic functionality.

Dependence of surface free energy on molecular orientation in polymer films

Surface free energy of mechanically drawn polycarbonate films was determined using contact angle measurements and shown to increase with orientation. The increase in polymer film surface free energy was attributed to increased polymer chain packing during orientation, supported by film density measurements, which provides enhanced intermolecular interactions. Surface free energy can therefore be increased by, or used to predict, polymer orientation.

Adhesion anisotropy between contacting electrospun fibers

The mechanical properties of electrospun fiber networks are critical in a range of applications from filtration to tissue engineering and are dependent on the adhesion between contacting fibers within the network. This adhesion is complex as electrospun networks exhibit a variety of contacts, including both cross-cylinder and parallel fiber configurations. In situ atomic force microscopy (AFM) was used to quantify the work of adhesion between a pair of individual electrospun polyamide fibers using controlled orientations and measurable contact areas. The work of adhesion was found to depend strongly on the fiber-fiber contact, with the separation of fibers in a parallel fiber configuration exhibiting considerably higher work of adhesion across a range of contact lengths than a cross-cylinder configuration. Our work therefore highlights direction-dependent adhesion behavior between electrospun fibers due to a suggested polymer chain orientation mechanism which increases net van der Waals interactions and indicates the variability of adhesion within a random electrospun fiber network.