Tissue scaffolds1, composite materials2, optical communications3, and conductive hybrid materials4 are areas of research utilizing specialized polymer fibers. Conventional methods for fiber fabrication include melt extrusion, spinning, drawing, casting and electrospinning. Most of the polymer fibers produced by these methods exhibit round cross-sections engendered by surface tension between the polymer and air during fabrication. However, fibers with nonround cross-sections may enhance the mechanical properties of composite materials5,6, increase surface area-to-volume ratios, control wetting or wicking7, and be utilized as waveguides8 or polarizers9.
Production of specialized polymer fibers by microfluidic systems employing one stream (sheath flow) to surround and shape another stream (core flow) are appealing because of the mild conditions and capacity for continuous production of highly reproducible fibers. Initial experiments produced round fibers with sizes dependent on the relative flow rates of the prepolymer and sheath fluids10-12. The discovery that grooves in the top and bottom of the microfluidic channel could deflect the sheath to produce a predetermined shape for the core stream13,14 led to technology for generating more complex fiber shapes10-12,15-17.
NRL investigators have demonstrated the following critical technical features13-21:
- A variety of shaping features can be used to direct the sheath fluid to shape the core stream: grooves or ridges can be configured as stripes, chevrons, or herringbones.
- A toolbox of these features can be mapped to the desired flow outcome.
- Microchannels can be created using lithography, molding, milling, or printing techniques. The substrate materials must not dissolve or erode in the prepolymer or sheath solutions, and for photoinitiated polymerizations, the external layers must be transparent to ultraviolet light.
- The shape created by a single set of shaping features can be altered by changing the flow rates through the channel. COMSOL Multiphysics simulations of fluid flow in the microchannels are capable of predicting the resulting fluid and fiber shapes.
- Matching the viscosity and phase (hydrophilicity) of the sheath and core fluids is critical to avoid buckling type instability, arising from variation in shear strain across the fluid interface. If there is a large viscosity or phase mismatch viscous buckling can occur, possibly deforming the final fiber shape or even clogging the microchannel.
- Fibers can be formed by casting or polymerization, but polymerization provides more control over shape.
- Polymerization (solidification of the core fluid) must occur prior to exiting the microchannel. However, slower polymerization within the channel may cause an increase in viscosity, affecting the fiber shape or even clogging the channel. The time and location of polymerization events must be carefully controlled.
- Due to their rapid reaction kinetics, photo-induced free radical polymerizations, especially thiol-based click chemistries, are particularly well suited for fiber production.
- The relative flow rates can be changed during fabrication to create nonuniform fiber diameters.
- Multiple groups of shaping features can be integrated into a single channel for the following reasons:
- To separate the shaping and sizing functions
- To create multilayer or hollow fibers
- To produce multiple fibers from a single microfluidic channel
- Liquid crystal mesogens incorporated in the polymer at very low concentrations exhibit birefringence under polarized light, suggesting that polymer molecules can be aligned along the axis of the fibers.
- Cells can be incorporated in biocompatible hydrogel prepolymers and survive the fabrication process with high viability22.
When fabricating polymer fibers using hydrodynamic focusing by a sheath stream to shape a prepolymer stream, selection of polymer materials is a practical first step. The appropriate polymers, corresponding initiator chemistries, and sheath fluids should be identified within the following guidelines:
- Polymer and sheath fluids are miscible and are of similar viscosity. For example, an aqueous monomer solution could utilize water as a viable sheath fluid, but could not employ hexane as the sheath fluid.
- The polymerization mechanism must have fast enough rate kinetics to solidify the core fluid after shaping and immediately before the fiber exits the channel.
After the materials have been selected, a microchannel to generate the desired fiber shape and size must be designed. To determine the required shaping features (stripes, herringbones, chevrons), computational fluid dynamics software can be utilized to predict the fluid flow patterns. The shaping features transport the sheath fluid around the core fluid. In general, stripes move the sheath fluid across the top and bottom of the channel from one side to the other, whereas herringbones and chevrons move the fluid away from the sides toward the top and/or bottom of the channel and then back toward the center of the channel directly under the point of the structure. The number of repetitive grooves in the top and bottom of the channel impacts the degree to which the sheath fluid is directed. The ratio of flow rates of the core and sheath fluid also mediate the effect. Simulations using COMSOL Multiphysics software have proven reliable in evaluating the interactions of the shaping features and flow-rate ratios to predict the cross-sectional shape. These simulations also provide useful insight into diffusion of solutes between the core and sheath with the size of the channel, viscosity, and flow rates proposed.
If a complex shape is desired, such as the “double anchor” described in Boyd et al.23, it is useful to separate the functions of shaping and sizing. A complex shape can be created with one set of features and then a strategically placed single-groove structure placed at the entrance of a second sheathing stream can be used to decrease the cross-sectional area of the polymerizable stream without significantly altering its shape.
Another example of complex microchannel design can generate multilayer fibers. In this design, sequential sets of shaping features and additional cladding fluids are introduced. These concentric flows can be solidified into solid core-cladding fibers or hollow tubes. An example of this device will be presented below.
Once the design of the microfluidic device has been chosen, the microchannel fabrication process can begin. Fabrication tools that can be used include soft lithography, CNC milling, hot embossing and 3D printing. Regardless of the tools used, it is important to realize that features accidently introduced into the wall of the microfluidic channel will also direct the sheath flow and may result in highly reproducible deviations in the cross-sectional shape of all fibers made using that device. Microchannel substrate materials should also be carefully selected to be physically robust, chemically inert, and resistant to UV-damage. For example, polydimethylsiloxane (PDMS) can be easily cast, provides gasket-like seals, and is UV transparent; PDMS is useful for the transparent top of the channel, but not the sides and bottom of the channel, which need more rigidity.
Ultimately, by introducing the properly selected core and sheath fluids at the flow rates predicted by the fluid dynamics simulations, the shaping features will generate the appropriate fluid profile and the downstream UV curing lamp will solidify the designed polymer fibers. Continuous extrusion of the polymerized fibers from the channel can provide reproducible fibers in lengths limited only by the volume of the fluid reservoirs.