In addition to the parallel hand brush-on method, we also
have developed an automated point-to-point serial drawing system. [3] The
positioning is done with an ultra-precision 3D translation system. Polymer is
dispensed through the same capillary tip that is used to pull the fiber. Fibers
down to 450 nm diameter have been drawn with this system. The panel on the right
shows a fabrication process and capillary for a suspended microfluidic channel
that is templated on a suspended fiber drawn by the automated drawing system.
The polymer droplets serve to define reservoirs. Gold electrodes are included
in the design. Voltages up to 100V have been applied to across the device and
fluorescent microbeads have viewed flowing through the capillary under a
microscope. [4]
Brush-on is done so fast that the fiber thinning is due
entirely to surface tension driven capillary thinning. The serial drawing is
generally much slower and both surface tension and viscoelastic effects (due to
the fiber solidifying through solvent evaporation during the pulling) causes
thinning. The brush-on thinning dynamics were modeled by the McKinley group prior to the start of this study. For the current study we are modeling the combination of
viscoelastic and surface tension based thinning, with the goal of determining
conditions for obtaining small fibers. The contour plot on the right summarizes
our first-pass results of this modeling. It is a map of resulting fiber thinning
as a function of processing parameter P (which is larger for faster solvent
evaporation rates) and capillary number Ca (which is larger for larger
stretching rates). Higher capillary numbers and lower values of P give the
most thinning from the initial diameter R0 of the polymer sample. Therefore,
with careful control of Ca and P a 1 mm thick polymer sample
could be thinned by a factor of 104 or to 100 nm. The model appears to make
physical sense, but the simulation has not been specialized for the material
parameters and functions (polymer concentration and
concentration-dependent viscosity)
of the polymer solutions used in our experiments. Once these parameters are
determined empirically, the model can be adjusted and the simulation rerun.
The UMass group has focused on the synthesis of
biodegradable polymers formed from hydrophobic lactic acid (PLA) and
hydroxybutyrate. The lactic acid materials are triblock copolymers containing a
central hydrophilic poly(ethylene oxide) segment while the hydroxybutyrate is a
homopolymer. We have also prepared and transferred block copolymers based on
poly(styrene-methyl methacrylate) and poly(alpha methyl styrene). The block
copolymers are excellent materials for forming nanoporous fibers and thin
films.
The brush-on method was used with 15% solution of the PLLA-PEO-PLLA in
chloroform to fabricate fibers with diameters ranging from 125 nm to >50 mm.
Then the fibers (see panel) were treated with (a) water, (b) heat and isopropyl alcohol, (c) and (d) heat and water which led to the formation of micrometer and nanometer
pores. The images show that the pore structure is quite sensitive to processing conditions. We are considering the use of these fibers as tissue scaffolds for
growing microcapillaries from endothelial cells. The field of organ
regeneration has yet to demonstrate successful growth of microcapillaries, and
without microcapillaries, the limited blood supply makes it impossible to regrow
many organs. The PLLA-PEO-PLLA triblock copolymer is both biocompatible and biodegradable,
and the ability to tailor the pore sizes and orientation would be useful in investigating
issues related to cell growth and the supply of growth factors through the
porous material.