This disclosure relates to an array of two-phase flow nozzles for spinning nanofibers
Manufacturing processes in which a material is formed by propelling a fluid composition from a nozzle by way of a fluid jet upon which the material solidifies into a desired form are known in the art. U.S. Pat. No. 8,666,854 discloses a film fibrillation process and apparatus for producing nanofibers a two-phase gas/polymer fluid mixture. The polymer and gas flow in the same channel. The gas flow spreads the polymer into a thin film. The thin film is fibrillated aerodynamically at the channel exit. Fiber fineness correlates with film thickness. All nozzles disclosed are axisymmetric. All nozzles disclosed have an annular channel with a decreasing annular radius in the direction of flow. This advantageously facilitates forming a single fiber forming air stream exiting the nozzle. However, it also reduces the wetted flow area in the direction of flow over which the polymer film flows causing it to thicken. The result is a wide distribution of fiber sizes with some larger microfibers being produced together with the finer nanofibers. This type of broad fiber size distribution is especially useful when seeking to produce a lofty fibrous web where the larger fibers provide resistance to compression. There is however a need for processes which can produce fibrous webs with a narrower range of fiber sizes.
U.S. Pat. No. 8,880,594 discloses coform fibrous materials and a method for making same using a modification to the axisymmetric nozzle design of U.S. Pat. No. 8,668,854. A flared nozzle provides a hollow annular channel, the center channel of which allows secondary materials to be aspirated into the air stream exiting the nozzle. The flared nozzle design is configured to provide an increased area of wetted flow to the polymer film in the direction of flow. This has the advantage of geometrically thinning the film as it moves down the two phase flow channel resulting in finer fibers. The flared design does not produce an aerodynamically coherent air stream exiting the nozzle.
The axisymmetric designs of the prior art are not easily adapted to scale up to multiple nozzles for producing wide uniform nonwoven webs.
In nozzle designs of the prior art, median fiber diameter is a function of polymer flow rates. Increasing polymer flow rates results in increases in fiber sizes. In film fibrillation processes, the polymer film thickens with increased flow rates and fibrillates into larger individual fibers. This has limited the industrial utility of nanofiber fabrication methods.
There is a need for a fiber spinning process an apparatus which incorporates both a gas driven fluid mixture and a geometric thinning of the polymer film to produce the finest possible fibers with a narrow diameter distribution.
There is also a need for a spinning nozzle design that can easily be scaled to provide uniform deposition of fibers across a conventional collection belt to create uniform nonwoven web.
There is further a need for methods for producing nanofibers at high flow rates.
There is also a need for methods for producing fine fibers at lower air flow rates.
The objective of the present disclosure is to provide a scalable apparatus composed of two-phase flow spinning nozzles that will combine a gas-polymer stratified two-phase flow into a thin polymer film and fibrillate the polymer film into nanofibers which can be uniformly deposited across a conventional collection belt to create nonwoven nanofibrous webs.
The current disclosure teaches a two-phase flow nozzle for forming and fibrillating a molten polymeric film into nanofibers including one or more first input orifices for a process gas; one or more second input orifices for a polymer melt; a flow channel including two or more channel walls and a monotonically decreasing flow area wherein the process gas and polymer melt are combined into a stratified two phase flow with the polymer melt formed into a film on one or more of the channel walls; one or more channel exit openings, each exit opening comprising an edge at which the process gas reaches sonic velocity or less and wherein the edge is configured to fibrillate the polymeric film into a stream of nanofibers.
In another embodiment, spacing of the polymer input orifices is configured so as to spread the film in a direction transverse to the flow direction as well as in the flow direction, thereby thinning the film.
In yet another embodiment, flow chamber geometry is configured to spread the film over an angle greater than thirty degrees.
In still another embodiment of the apparatus, the channel exit opening comprises grooves configured to split the polymer film into a plurality of individual polymer streams.
In yet another embodiment of the apparatus, the channel exit opening increases wetted polymer flow area further thinning the polymer film by geometrical modifications comprising grooves, sawtooths, sinusoids, ellipsoids, square waves, rectangular waves, pulse waves and triangular waves.
In still another embodiment, nanofibers cross section is not circular.
The current disclosure also teaches an apparatus for forming and fibrillating a molten polymeric film into nanofibers including a plurality of two-phase flow spinning nozzles arranged in a substantially linear array each nozzle including one or more first input orifices for a process gas; one or more second input orifices for a polymer melt, a flow channel comprising two or more walls where the process gas and polymer melt are combined into a stratified two phase flow with the polymer melt formed into a film on one or more of the channel walls; one or more channel exit openings, each exit including an edge at which the process gas reaches sonic velocity or less and wherein the channel exit opening edge is configured to fibrillate the polymeric film into a stream of nanofibers.
In one aspect of the apparatus, mass ratio of air flow rate to polymer flow rate required to produce nanofibers is less than about 50.
In another aspect of the apparatus, the apparatus is configured to produce non-woven nanofibers at flow rates greater than 1 gram per minute per centimeter.
In one embodiment, the apparatus includes a moving surface positioned at a set distance from the exit opening edge of the flow channel for collecting the nanofibers
The disclosure also teaches a process for forming and fibrillating a molten polymeric film into nanofibers using a substantially linear array of two-phase flow nozzles the process including the steps of introducing a process gas into one or more first orifices of each nozzle; introducing a polymer melt into one or more second orifices of each nozzle; combining the process gas and polymer melt in a stratified two phase flow inside a flow channel comprising two or more channel walls and one or more channel exit openings, each exit opening comprising an edge, wherein the flow channel has a monotonically decreasing flow area; forming a polymer film on one or more of the channel walls; accelerating the process gas to sonic velocity or less and fibrillating the polymer film at the exit opening edge into a stream of nanofibers.
In one aspect of the process, spacing of the polymer input orifices is configured so as to spread the polymer film in a direction transverse to the flow direction as well as in the flow direction, thereby thinning the film.
In another aspect of the process, flow chamber geometry is configured to spread the polymer film over an angle greater than thirty degrees.
In still another aspect of the process, the channel opening comprises grooves configured to split the polymer film into a plurality of individual polymer streams.
In yet another aspect of the process, the channel exit opening increases the wetted polymer flow area further thinning the polymer film by geometrical modifications selected from the list comprising grooves, sawtooths, sinusoids, ellipsoids, square waves, rectangular waves, pulse waves and triangular waves.
In yet another aspect of the process of the disclosure, nanofibers cross section is not circular.
In an aspect of the process of the disclosure, mass ratio of air flow rate to polymer flow rate required to produce nanofibers is less than about 50.
In another aspect of the disclosed process, the nanofibers are produced at a rate of at least 1 gram per minute per centimeter.
In still another aspect of the disclosure, the process comprises the step of collecting the nanofibers on a moving surface positioned at a set distance from the exit opening edge of the flow channel.
In a further embodiment, the disclosure provides a method and apparatus for producing a non-woven fibrous web with high uniformity, high porosity, small pore size and high surface area.
In various exemplary embodiments, the spin nozzle, apparatus, and method of the present disclosure may permit production of nonwoven fibrous webs containing nanofibers with a narrow distribution in fiber diameter. Other exemplary embodiments of the present disclosure may have structural features that enable their use in a variety of applications; may have exceptional absorbent and/or adsorbent properties; may have exceptional thermal resistance, may exhibit high porosity, high fluid permeability, and/or low pressure drop when used as a fluid filtration medium and may be manufactured in a cost-effective and efficient manner.
In other exemplary embodiments, the disclosure provides a process and apparatus for the production of relatively strong composite nanofibrous webs of discontinuous fibers made of polymeric materials for use as high efficiency filtration media to purify water and other fluids.
In other exemplary embodiments, the disclosure provides an apparatus and method to make high efficiency polymeric composite filtration media incorporating nanofibers which incur relatively low pressure losses associated with the flow of water and other liquids through such media.
In still further embodiments, the disclosure provides a process and apparatus for the production of relatively strong composite fibrous webs of discontinuous nanofibers.
Another aspect of the invention is to provide a more efficient means to spin nanofibers via film fibrillation from polymer melt using a heated gas stream as the working fluid.
Another aspect of the invention is to provide a spinning nozzle which allows for precise control of the exit gap which assures a very thin film, and minimizes the gas flow requirement for fine fiber production.
Another aspect of the invention is to provide a high throughput means to convert a single melt feed stream to nanofibers.
Another aspect of the invention is to provide a nanofiber spinning process with minimal air consumption.
Another aspect of the invention is to provide a two phase flow nozzle with an aerodynamically coherent air stream exiting the nozzle such that the fiber containing air stream can be blended with the exit streams of other nozzles.
Another aspect of the invention is to provide a spin nozzle design that can easily be scaled with multiple nozzles comprising a spin beam which can deposit fibers uniformly across a conventional collection belt to create uniform nonwoven web.
Another aspect of the invention is to provide a spin nozzle that facilitates activating or shutting down spin beam segments to allow production of nonwoven webs of varied widths.
Another aspect of the invention is to provide a spin nozzle design that facilitates fiber and web functionalization by adding particulates via coforming capability.
Various aspects and advantages of exemplary embodiments of the present disclosure have been summarized. The above summary is not intended to fully describe or limit each illustrated embodiment or every implementation of the present disclosure. The Drawings and the Detailed Description that follow more particularly exemplify certain preferred embodiments using the principles disclosed herein.
“Two Phase Flow Nozzle” means a spinning nozzle where a process gas and a polymer melt are introduced and combined into a two-phase gas-polymer flow.
“Substantially Linear” means a rectangle enclosing the element or a projection of the element has a length to width ratio of 2 or greater.
“Flow Channel” means a duct or passage wherein polymer melt and process gas flow simultaneously as a stratified two phase flow in a manner that produces a thin polymer film which forms fibers upon exiting the duct or passage.
“Spinning Beam” means an assembly of fiber forming flow channels configured to issue a substantially linear spatial array of fibers as across a web forming collector.
Spreading Angle” means the angle defined by 2 times the angle whose tangent is ½ the width of the lateral spread of the polymer film exiting the fiber forming flow channel divided by the centerline distance of the flow exit from the point of polymer entry.
Disclosed herein is a process and apparatus for the formation of fine fibers and nanofibers by means of film fibrillation of a two-phase polymer-gas flow. Without being bound by theory, the apparatus combines a polymer melt stream and a process gas stream as a working fluid in a single flow channel to form a stratified two phase flow. The process gas stream is introduced into the flow channel at the channel entrance through a first orifice. The polymer melt is introduced at the wall of the flow channel near the channel entrance through a second orifice and is moved through the channel by gas pressure and the shearing force of the gas flow. It has been unexpectedly been found that a shearing gas flow can be configured to thin a polymer-gas film transversally to the direction of flow as well as in the direction of flow, resulting in a uniform distribution of nanofibers. In various embodiments, a spinning nozzle extrudes a stratified polymer-gas two phase flow to a thin polymer film into a flow channel configured to spread the polymer film in the direction of flow to a total angle of from 30 to 60 degrees from its source. Multiple adjacent nozzles may be combined into a pack assembly providing for a uniform distribution of nanofibers across the width of a web forming apparatus.
In an embodiment of the disclosure, the flow channel is constructed with a monotonically decreasing flow area to accelerate the gas and polymer flows in a manner which spreads the polymer film not only in the direction of flow, but in a direction transverse to the general flow direction resulting in advantageous additional thinning of the polymer film. The stratified two phase flow exits the flow channel at a downstream exit end comprising a thin, substantially linear slot or gap. The gas velocity is high enough to induce fiber formation via film fibrillation immediately as the combined flow leaves the flow channel and enters free space. It is believed that the fineness of the resulting fibers is determined by the thinness of the polymer film. The innovative transverse spreading and thinning of the film in addition to thinning in the flow direction result in a surprisingly efficient means of producing sub-micron nanofibers as shown in the examples below.
An embodiment of the flow channel is illustrated in
The process gas flow enters the apparatus through an entrance 5 and flows to the channel entrance chamber 6. The entrance chamber has width, Wo, and a height, Ho. The polymer melt enters through the polymer port 6 and flows through a metering capillary 7 into the entrance chamber 6 from which it is forced by the gas flow to flow and spread along a spreading surface 3 following the contour 8.
The flow channel geometry is designed such that the flow area for the stratified two phase flow of gas and polymer melt monotonically decreases from the channel entrance as follows: Channel width, W, and channel height, H, both change and are function of X, the centerline distance from the channel entrance, hence, W(x) and H(x). The channel width, W(x), increases according to a function which is chosen to be compatible with combined polymer and gas fluid mechanics so as to spread the gas and polymer flows together and without flow anomalies such as recirculation zones. If the channel width increases too rapidly or too much, the polymer film may not follow or adequately cover the spreading surface. The result can be undesirable distributions of fibers both in size and spatially. The efficient use of process gas can suffer also as some gas will bypass the areas covered with polymer film. For the examples herein, the channel width. W(x), increases linearly with X according to a spreading angle, θ.
The channel flow area, A(x), is assigned a monotonically decreasing function of X. For the examples herein, the channel flow area, A(x), decreases linearly with distance X. Since the channel flow area is given by the product of channel width and height, W(x)*H(x), specifying the channel width and area determines the channel height at any distance, X, from the channel entrance resulting in the contour 8 of the spreading surface.
The utility of the fiber forming flow channel of this disclosure is not limited to the examples presented above. Those skilled in the art will know that other configurations are possible depending on process and product requirements.
A second embodiment of the flow channel is illustrated in
Process Description
A two-phase flow nozzle 101 for spinning fibers is positioned at a distance 111 relative to a collecting surface 112, as illustrated in
A cross-section view A-A of nozzle 101 is shown in
Linear Array
Individual spinning nozzles extrude a substantially planar polymer thin film. These spinning nozzles may be readily configured in an array that can produce nanofibers uniformly across the width of a web forming apparatus. In an embodiment of the disclosure, the array is linear.
An embodiment of an apparatus (cross machine direction and throughput) for making nanofibers is shown in
Nozzle 201 is located a distance 210 from a fiber collecting surface 211. Nozzle 201 is shown parallel to the cross machine direction; however it can be located at any angle. Nozzle 201 is comprised of modular sections such that the process width in the cross machine direction is scalable to a desired product width. Air is injected into chamber 215 through ports 203. Polymers are injected into chambers 217 and 218 through ports 204 and 216, respectively (see
The individual flow cell described above has proven highly efficient and capable of producing submicron fibers at a rate of 7.2 grams per minute and higher from a single polymer feed capillary. Multiple linear arrays of fiber forming cells can be used to meet or exceed conventional melt blowing throughputs. Multiple linear arrays of fiber forming cells can be used to meet economically required throughputs.
Edge Geometry
Various edge geometry configurations are illustrated in
Other configurations of the edge geometry are illustrated in
Atactic polypropylene (Sigma Aldrich Mw 12,000, Mn 5000) was fed to a 19 mm Brabender single screw melter, heated to 181 Deg C. and fed to a single flow channel of the two-phase flow nozzle of
Atactic polypropylene (Sigma Aldrich Mw 12,000, Mn 5000) was fed to a 19 mm Brabender single screw melter, heated to 181 Deg C. and fed to a single flow channel of a two-phase flow nozzle of
Atactic polypropylene (Sigma Aldrich Mw 12,000, Mn 5000) was fed to a 19 mm Brabender single screw melter, heated to 181 Deg C. and fed to a single flow channel of nozzle of
An extruder (¾ inch Laboratory Extruder from C. W. Brabender, Valley Forge, Pa.) was used to supply a polymer mixture to a spin nozzle having configuration 101 as shown in