1. Field of Invention
This method of fiber production relates in general to electrospinning and specifically to MEMS (Micro ElectroMechanical Structures). Using current integrated circuit manufacturing processes, it is feasible that a tiny, compact, self-contained device could be constructed to carry out the process of electrospinning fibers. One of the great benefits of using a MEMS device is that the voltage required to produce a “so called” Taylor Cone would be substantially reduced, and the hydrostatic feed system could be incorporated into the MEMS device through the use of passive wick technology. The incorporation of holey fibers into a MEMS device will also be discussed. The electrospray needle sources could be easily fabricated to produce co-axial arrangements to permit the electrospinning of two or more chemical compounds to form unique and complex fibers.
2. Background Description of Prior Art
There are several current methods of producing fibers for later use in various products; however, there is no easy way to mechanically produce microfibers (10−6 m mean diameter) and even smaller nanofibers (10−9 m mean diameter). The microfibers are fibers with a mean diameter of millionths of a meter (um) and the nanofibers are fibers with a mean diameter of billionths of a meter (nm). To give an example of how small that is, a standard sheet of printer paper has an average thickness of about 0.003″ or 0.0762 mm, which is equal to 76.2 μm and 76,200 nm. The wavelength of red light is equal to approx. 690 nm. It is all but impossible to construct a mechanical means or spinning a fiber that has a mean diameter of micrometers, let alone nano-meters! One simple way to do this impossible feat is to use the proven technology of electrospray. Through the use of electrospray technology incorporated into a MEMS device, it is possible to produce an extremely fine fiber that meets this criterion of producing micrometer and nanometer sized diameters.
Electrostatic fiber spinning, or “electrospinning,” is a technology that uses electric fields to produce nonwoven materials which are unparalleled in their porosity, high surface area, and the fineness and uniformity of their fibers. The diameters of electrospun fibers are typically hundreds of nano-meters, one to two orders of magnitude smaller than fibers produced by conventional extrusion techniques. These fibers are attracting considerable interest in a wide range of applications, including filters, membranes, composites and biomimetic materials. Despite this surge in interest, the essential features of the process responsible for the formation of such fine fibers have proved elusive to both scientific understanding and engineering control.
Typically the sub-micron diameter fibers are produced from an aqueous solution by electrospinning and collected as a nonwoven fabric when a charged fluid jet is accelerated down an electric field gradient, solidified, and deposited onto a grounded collector. Similar fibers have been manufactured from over 30 different kinds of polymers in recent years. By contrast, synthetic polymer fibers produced by conventional extrusion-and-drawing processes are typically 10 um to 500 um in diameter, and are collected on spools for forming yarns or woven textiles. Controlling the fiber properties requires understanding how the electrospinning process transforms a millimeter-diameter fluid stream into solid fibers four orders of magnitude smaller in diameter. In the conventional view, electrostatic charging of the fluid at the tip of a nozzle results in the formation of the well-known Taylor cone, from the apex of which a single fluid jet is ejected. As the jet accelerates and thins in the electric field, radial charge repulsion results in “whipping about” of the jet, in a process known as “splaying.” The final fiber size is determined by several factors, such as the electrospray voltage, concentration of solvent to solute, and distance to target. During electrospinning it is normal for the rapid growth of a nonaxisymmetric, or “whipping,” instability that causes bending and stretching of the jet. At low fields, the jet uniformly thins and extends from the nozzle to the collector, while at high fields, and after traveling a short distance, the jet becomes unstable and “whips about”. The use of MEMS devices will enable an effective low field electrospray to be used for electrospinning. An effective means of controlling the “whipping” instability has already been addressed by Dr. John B. Fenn. Dr. Fenn is considered to be an “elder” in the area of electrospray research, and recently won the 2002 Nobel Prize in Chemistry for his pioneering work in electrospray. He is regarded as the “E. F. Hutton” of electrospray—when he speaks, everyone listens! Dr. Fenns idea was to use an alternating voltage at the source to prevent charge buildup on individual fibers. This prevents the typical non-uniform distribution in the laying of electrospun fibers. With the use of tiny MEMS devices, the lower field will enable stable fibers that will not be affected by any “whipping” instability. Another innovation in the field of electrospray and electrospinning technology that was made by Dr. John B. Fenn was to use a “wick” in place of a costly hydrostatic feed pump. The wick is a self-regulating liquid feed system with no moving parts, and can accurately control picoliters (10−12 L) of fluid. The wick used for electrospray and electrospinning applications could be an internal one or an external one. If an internal wick is used, then the wicking material would have to be enclosed into a needle or some structural material to hold it. This is very difficult when dealing with needles that have diameters in the micrometer range. A better solution would be to use a recent discovery of utilizing special glass optical fibers that contain tiny holes running the length of the fiber, known as “Holey Fibers”. These holey fibers could contain upwards of 200 holes with hole diameters ranging from sub-micron sizes to tens of microns. Together with a suitable MEMS device, single holey fibers or a plurality of holey fibers could facilitate the electrospinning process. When dealing with an externally wetted wick, no actual wicking material is used; the treated surface of a small needle will function adequately. The MEMS devices will benefit greatly from this technology. While the preferred embodiment is a surface that has been treated so as to form a rough surface that can “wick” a solvent-polymer combination, patent priority extends to a MEMS device where nano nozzles are created in which the solvent-polymer solution is delivered via a hydrostatic feed mechanism. The nano fluidic prior art includes nano spray nozzles that have been developed that are hydrostatically fed for electrospray analytical applications, but not for the electrospinning application as disclosed in this patent disclosure.
To recap the electrospinning process, a polymer, in this case example collagen is dissolved by a suitable solvent and injected under hydrostatic pressure into a conductive needle or capillary. A DC potential of preferably 500 to 1,000 volts, which can be greater or lower than this value depending on the spray source to target gap, is maintained between the electrospray source and a suitable target located at a distance away from the needle sufficient to preclude production of a corona or arc. The voltage is adjusted according the distance, desired fiber diameter and structure. Voltage difference between injection needle and target suited to the given solvent conductivity, polymer, and flow rate, enable a resulting electrostatic field at the needle tip that results in the formation of a Taylor Cone from the tip which issues a micron sized jet diameter which is attracted to, and impacts with, the ground cathode target. Evaporation of solvent from this jet results in a polymer strand of collagen or other polymer. The accumulation of such strands creates a “mat” of polymer having a homogenous diameter ranging from tens of microns or more down to tens of nanometers or less, depending on the concentration and nature of solute, the conductivity and viscosity of liquid, and the potential difference between the needle and target. It has been shown by Wnek et al. of Virginia Commonwealth University (VCU), that electrospun collagen fibers can be produced down to 100 (+/−40) nano meters in diameter. Calf skin dissolved in a suitable solvent was electrospun, and upon Transmission Electron Microscopy (TEM) examination, revealed the same banded appearance characteristic of native polymerized collagen. Various polymers studied yielded fiber diameters in the range of 0.1 to 10 um. It should be noted that nano-extrusion rather than electrospinning of the polymer are an alternative in certain instances.
Polymer mats produced by this process can have diameters up to tens of microns and thickness of up to hundreds of microns, depending on deposition time. Similarly, it has been found that polymers such as collagen for creating a suitable corneal mat as part of this invention can be derived from a variety of sources. In the preferred embodiment, synthetic collagen such as that manufactured by FibroGen of San Francisco, Calif., is dissolved by a solvent such as 1,1,1,3,3,3 hexaflouro-2-propanol (HFIPA) and electrospun into a fibril diameter of preferably 65 nanometers and spun into a mat that can be trimmed to desired final dimensions. Laser cutting or trimming is preferably employed since fibril terminations must be severed and should not be excessively frayed or tangled. Tangling or fraying can affect bonding to some surfaces. While the resulting polymer “mat” consists of disorganized fibrils, this disorganization can be remedied by using a varying polarity (AC) high voltage source in place of a constant DC potential in the spraying process.
In the MIT lab for their nano thruster propulsion research, Dr. Martinez-Sanchez and Dr. Velasquez investigated the wetting properties of several materials such as bare Silicon (with various roughness'), Silicon Dioxide (SiO2), Silicon Nitride (Si3N4), Aluminum and black Silicon to various ionic liquids. To modify the wetting properties of regular Silicon, MIT used a surface modification technique. Surface modification techniques can be of physical, chemical or radiative nature. In this case, plasma (radiative) was employed to modify the surface roughness and wetting energy. In particular, experiments proved most successful with black Silicon. Black Silicon results from exposing a regular Si wafer to a plasma dry etch with a chlorine chemistry. The end result is a strong roughening of the surface. The process is conformal, thus translating into good step coverage for microfabricated structures.
10 Main structure of the silicon MEMS device housing a two dimensional array of electrospray needles.
10 Black silicon SEM image after five minutes of plasma exposure
20 Black silicon SEM image after ten minutes of plasma exposure
10 SEM image of group of individual electrospray emitters, specifically the top corner where the electrospray would emanate from.
20 Sidewall of treated silicon of a single “volcano like” electrospray emitter.
10 Close up view showing the structure of a single silicon electrospray needle that makes up the MEMS array.
20 Close up view detailing the sharp pointed tip of a single silicon electrospray needle.
SEM (Scanning Electron Microscope) close-up of “Volcano-like” emitter
10 SEM images of the microfabricated chip with pointed “pencil like” emitters before wetting of polymer-solvent solution
20 SEM images of the microfabricated chip with pointed “pencil like” emitters after wetting of polymer-solvent solution
Number | Date | Country | |
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60526879 | Dec 2003 | US |