Nanofiber Fabric
The nanofiber fabric with selectively applied adhesives or graphene sheets addresses the issue of property inhibition in existing configurations by maintaining thermal and electrical conductivity and transparency, ensuring effective substrate integration.
Patent Information
- Application Number
- JP2023152258
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2018-05-16
- Filing Date
- 2023-09-20
- Publication Date
- 2025-01-21
- Estimated Expiration
- 2039-03-26
AI Technical Summary
Existing nanofiber thread configurations often embed nanofibers within adhesives or polymers, which inhibit the beneficial properties such as thermal and electrical conductivity, and reduce infrared radiation transparency.
A nanofiber fabric is created with selectively positioned adhesives or non-adhesive attachments like graphene sheets, allowing the nanofibers to maintain their orientation and position while adhering to substrates, thereby preserving their properties.
The solution enables the nanofiber fabric to maintain thermal, electrical conductivity, and infrared transparency by minimizing adhesive contact, allowing direct contact with substrates and enhancing substrate integration.
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Abstract
Description
[Technical field]
[0001] The present disclosure relates generally to nanofibers. In particular, the present disclosure relates to nanofiber fabrics made from nanofiber yarns. [Background technology]
[0002] Nanofiber forests, consisting of both single-walled and multi-walled nanotubes, can be drawn into nanofiber ribbons or nanofiber sheets. Before being drawn, the nanofiber forest contains a layer (or several stacks) of nanofibers that are parallel to each other and perpendicular to the surface of the growth substrate. Upon being drawn into a nanofiber sheet, the orientation of the nanofibers changes from perpendicular to parallel to the surface of the growth substrate. The nanotubes in the drawn nanofiber sheet connect to each other in an end-to-end configuration to form a continuous sheet in which the longitudinal axes of the nanofibers are parallel to the plane of the sheet (i.e., parallel to both the first and second major surfaces of the nanofiber sheet). The thickness of an individual nanofiber sheet can range from a few microns to tens of nanometers. The nanofiber sheets can then be spun into nanofiber yarns. Summary of the Invention
[0003] Example 1: a first plurality of nanofibers oriented in a first direction; a second plurality of nanofibers oriented in a second direction different from the first direction, the second plurality of nanofibers contacting the first plurality of nanofibers at a plurality of junctions; an adhesive deposit on at least a portion of the plurality of joints; The nanofiber fabric comprises:
[0004] Example 2 includes the subject matter described in Example 1, wherein the angle between the first direction and the second direction is between 45° and 135°.
[0005] Example 3 includes the subject matter of example 1 or example 2, wherein the angle between the first direction and the second direction is between 60° and 120°.
[0006] Example 4 includes the subject matter of any of the preceding examples, wherein the nanofiber fabric is transparent to infrared light.
[0007] Example 5 includes the subject matter described in Example 4, wherein the width of the gap formed between the nanofibers oriented in a first direction and the nanofibers oriented in a second direction in the nanofiber fabric is 1 μm to 10 mm.
[0008] Example 6 includes the subject matter of any of the preceding examples, wherein the nanofiber fabric acts as a barrier to electromagnetic interference.
[0009] Example 7 includes the subject matter of any of the preceding examples, wherein at least one of the nanofibers of the first plurality and the second plurality comprises a twisted nanofiber yarn.
[0010] Example 8 includes the subject matter described in Example 7, wherein the twisted nanofiber yarn comprises a nanofiber false twist yarn.
[0011] Example 9 includes the subject matter of any of the preceding examples, wherein the nanofibers of at least one of the first and second plurality comprise a coiled nanofiber yarn.
[0012] Example 10 includes the subject matter of Example 9, wherein the coil of the coiled nanofiber yarn, when placed in contact with a substrate having a three-dimensional topography, is at least partially stretched, thereby enabling at least a portion of the first plurality of nanofibers and the second plurality of nanofibers to maintain their orientation and position relative to one another.
[0013] Example 11 includes a frame having at least a portion of ends of the first plurality of nanofibers and the second plurality of nanofibers disposed thereon; This includes the subject matter described in any of the preceding examples, wherein the adhesive deposit is present on at least a portion of ends of the first plurality of nanofibers and the second plurality of nanofibers, the ends being disposed on the frame.
[0014] Example 12 includes the subject matter of any of the preceding examples, wherein at least a portion of the first plurality of nanofibers and the second plurality of nanofibers are infiltrated with an adhesive.
[0015] Example 13 includes the subject matter of Example 12, further comprising a first plurality of adhesive fillets on nanofibers of the first plurality of nanofibers in contact with corresponding nanofibers of the second plurality of nanofibers.
[0016] Example 14 relates to a substrate in contact with the nanofibers of the second plurality of nanofibers; a second plurality of adhesive fillets in contact with both the nanofibers of the second plurality of nanofibers and the substrate; The subject matter described in Example 13 further comprises:
[0017] Example 15 includes the subject matter of any of the preceding examples, further comprising a release liner having an adhesion energy of less than 40 dynes / cm, the release liner being present on at least one side of the nanofiber fabric.
[0018] Example 16 includes the subject matter of Example 15, wherein the release liner comprises a deformable sheet configured to deform to conform to a substrate having a three-dimensional topography.
[0019] Example 17 includes the subject matter described in any of the preceding examples, wherein the adhesive deposit includes a sol-gel precursor.
[0020] Example 18 includes the subject matter described in Example 17, wherein the sol-gel precursor includes a silicon dioxide precursor and a solvent.
[0021] Example 19 includes the subject matter of any of the preceding examples, wherein the first plurality of nanofibers are interwoven with the second plurality of nanofibers to form the nanofiber fabric.
[0022] Example 20 includes the subject matter of any of the preceding examples, wherein the first plurality of nanofibers is disposed on one side of the second plurality of nanofibers to form the nanofiber fabric.
[0023] Example 21 is a method for manufacturing a fluororesin comprising the steps of: This invention includes the subject matter described in any of the preceding claims, including carbon nanotubes.
[0024] Example 22 includes the subject matter of example 21, wherein the carbon nanotubes include multi-walled carbon nanotubes.
[0025] Example 23 includes the subject matter of any of the preceding examples, wherein the first plurality of nanofibers and the second plurality of nanofibers have diameters between 10 nm and 1 μm.
[0026] Example 24 is a release liner comprising a backing material and a first adhesive having a first adhesive strength; a plurality of nanofiber yarns disposed on the first adhesive of the release liner, the nanofiber yarns being twisted and coiled nanofibers; a second adhesive disposed on at least one surface of the nanofiber yarn or within the nanofiber yarn between the twisted and coiled nanofibers, the second adhesive having a second adhesive strength greater than the first adhesive strength; The nanofiber fabric comprises:
[0027] Example 25 includes the subject matter of Example 24, wherein the plurality of nanofibers includes a first plurality of parallel nanofibers oriented in a first direction and a second plurality of parallel nanofibers oriented in a second direction.
[0028] Example 26 includes the subject matter of example 24, wherein the angle between the first direction and the second direction is between 45° and 135°.
[0029] Example 27 includes the subject matter of example 25, wherein the angle between the first direction and the second direction is between 60° and 120°.
[0030] Example 28 includes the subject matter of any of Examples 24-27, wherein the nanofiber fabric is transparent to infrared radiation.
[0031] Example 29 includes the subject matter of any of Examples 24-28, wherein the nanofiber fabric acts as a barrier to electromagnetic interference.
[0032] Example 30 includes the subject matter of any of Examples 24-29, wherein the nanofiber yarn twist and coil is at least partially elongated when placed in contact with a substrate having a three-dimensional topography, thereby enabling the nanofiber yarns to maintain their orientation and position relative to one another.
[0033] Example 31 includes the subject matter of any of Examples 24-30, wherein the adhesion energy of the first adhesive is less than 40 dynes / cm and the release liner is present on at least one side of the nanofiber fabric.
[0034] Example 32 includes the subject matter of Example 31, wherein the release liner comprises a deformable sheet configured to deform to conform to a substrate having a three-dimensional topography.
[0035] Example 33 includes the subject matter of any of Examples 24-32, wherein the adhesive comprises a sol-gel precursor.
[0036] Example 34 includes the subject matter described in example 33, wherein the sol-gel precursor includes a silicon dioxide precursor and a solvent.
[0037] Example 35 includes the subject matter described in example 33, wherein the sol-gel precursor includes an aluminum oxide precursor and a solvent.
[0038] Example 36 includes the subject matter described in example 33, wherein the sol-gel precursor includes an yttrium oxide precursor and a solvent.
[0039] Example 37 includes the subject matter described in Example 33, wherein the sol-gel precursor includes a zinc sulfide precursor and a solvent.
[0040] Example 38 includes a method for fabricating a nanofiber fabric comprising: disposing a first plurality of nanofibers oriented in a first direction over a second plurality of nanofibers oriented in a second direction different from the first direction, wherein the first plurality and the second plurality contact at a plurality of junctions to form a nanofiber fabric; applying an adhesive to at least some of the plurality of joints; placing the nanofiber fabric in contact with a release liner; The method includes:
[0041] Example 39 includes the subject matter of Example 38, further comprising conforming the nanofiber fabric and the release liner to the three-dimensional surface, wherein the release liner and nanofiber fabric conform to the three-dimensional surface.
[0042] Example 40 includes the subject matter of Example 39, wherein the nanofiber fabric conforms to features on the three-dimensional surface that are at least 10 μm in size.
[0043] Example 41 includes the subject matter of example 39, further comprising removing the release liner while leaving the nanofiber fabric on the three-dimensional surface.
[0044] Example 42 includes the subject matter of Example 39, wherein the first plurality of nanofibers and the second plurality of nanofibers maintain their orientation relative to one another when conformed to the three-dimensional surface.
[0045] Example 43 includes the subject matter of Example 39, further including an electrical contact established using a nanofiber fabric between two electrically insulated conductors on the three-dimensional surface.
[0046] Example 44 includes the subject matter of any of Examples 38-43, wherein at least a portion of the first plurality of nanofibers or the second plurality of nanofibers is a twisted, coiled nanofiber yarn.
[0047] Example 45 includes the subject matter of any of Examples 38-43, wherein applying the adhesive further includes adding an aerosol of adhesive to the nanofiber fabric, the aerosol accumulating on at least some of the joints of the plurality of joints.
[0048] Example 46 is a method for applying the adhesive, infiltrating nanofibers of the first plurality of nanofibers and the second plurality of nanofibers with the adhesive; forming an adhesive fillet on at least a portion of said plurality of joints; The subject matter described in any of Examples 38-43 further includes:
[0049] Example 47 includes the subject matter of example 46, wherein the adhesive comprises a sol-gel precursor.
[0050] Example 48 includes the subject matter described in example 47, wherein the sol-gel precursor includes an aluminum oxide precursor and a solvent.
[0051] Example 49 includes the subject matter of example 47, wherein the sol-gel precursor includes an yttrium oxide precursor and a solvent.
[0052] Example 50 includes the subject matter described in example 47, wherein the sol-gel precursor includes a zinc sulfide precursor and a solvent.
[0053] Example 51 includes the subject matter of any of Examples 38-50, wherein placing a first plurality of nanofibers oriented in the first direction on top of a second plurality of nanofibers in a second direction different from the first direction further includes interweaving the first plurality of nanofibers with the second plurality of nanofibers to form the nanofiber fabric.
[0054] Example 52 is A substrate; Nanofibers disposed on the substrate; and a graphene sheet having a central portion, a first side portion and a second side portion opposite the central portion, a first end portion bonded to the first side portion, and a second end portion bonded to the second side portion; Equipped with The central portion of the graphene sheet is in contact with a side of the nanofiber opposite the substrate, and the first and second ends are in contact with the substrate, resulting in a nanofiber assembly.
[0055] Example 53 includes disposing nanofibers on a substrate; suspending the graphene sheets in a solvent to form a graphene suspension; applying the graphene suspension to the nanofibers on the substrate such that at least one of the graphene sheets in the suspension attaches the nanofiber to the substrate. [Brief description of the drawings]
[0056] [Figure 1] FIG. 1 shows an adhesive film having nanofibers encapsulated therein, the adhesive film and nanofibers being adhered to a substrate on one side and to a polymer sheet on the other side. [Diagram 2] 1 is an image showing an example of a forest of nanofibers on a substrate according to one embodiment. [Diagram 3] FIG. 1 is a schematic diagram of a reactor for growing nanofibers, according to one embodiment. [Figure 4A] FIG. 2 is a diagram of a nanofiber sheet in one embodiment, illustrating the relative dimensions of the sheet and showing, in a schematic diagram, the nanofibers within the sheet oriented end-to-end in a plane parallel to the surface of the sheet. [Figure 4B] FIG. 4B is an image of a nanofiber sheet pulled laterally from a nanofiber forest, with the nanofibers oriented end-to-end as shown in the schematic diagram in FIG. 4A. [Figure 5A] FIG. 2 is a close-up scanning electron microscope (SEM) view of a nanofiber yarn that includes nanofibers twisted together and also includes a coil, according to one embodiment. [Figure 5B] FIG. 1 illustrates, in one embodiment, a first plurality of nanofiber yarns oriented in a first direction and joined to a second plurality of nanofiber yarns oriented in a second direction at an angle θ to the first direction, thus forming a nanofiber textile. [Figure 5C] In one embodiment, a diagram showing the nanofiber fabric of FIG. 5B on a surface having a three-dimensional (3D) topography, where the nanofibers of the nanofiber fabric maintain their orientation and position relative to one another even when placed on the three-dimensional surface. [Figure 6A] FIG. 2 is a plan view of a free-standing nanofiber fabric in one embodiment, the free-standing nanofiber fabric being attached to a frame around the perimeter of the free-standing nanofiber fabric. [Figure 6B] FIG. 6B is a cross-sectional view of the nanofiber fabric of FIG. 6A. [Figure 6C] FIG. 6C is a cross-sectional view of the nanofiber fabric of FIGS. 6A and 6B, according to one embodiment, removed from the frame and placed on a substrate. [Figure 7A] FIG. 2 is a plan view of one embodiment of a free-standing nanofiber fabric adhered to a frame with multiple adhesive deposits disposed at inter-nanofiber bonds. [Figure 7B] FIG. 7B is a cross-sectional view of the nanofiber fabric of FIG. 7A. [Figure 7C] FIG. 7C is a cross-sectional view of the nanofiber fabric of FIGS. 7A and 7B, according to one embodiment, removed from the frame and placed on a substrate. [Figure 8A] FIG. 2 is a top view of one embodiment of a free-standing nanofiber fabric adhered to a frame, with adhesive permeating the nanofibers of the nanofiber fabric. [Figure 8B] FIG. 8B is a cross-sectional view of the nanofiber fabric of FIG. 8A. [Figure 8C] FIG. 8C is a cross-sectional view of the nanofiber fabric of FIGS. 8A and 8B, according to one embodiment, removed from the frame and placed on a substrate. [Figure 9A] 1 is a schematic cross-sectional view of a nanofiber attached to a substrate by a graphene sheet, according to one embodiment. [Figure 9B] 1 is a scanning electron microscope (SEM) image of graphene sheets attaching nanofibers to a substrate in one embodiment. [Figure 9C] 1 is a scanning electron microscope (SEM) image of graphene sheets attaching nanofibers to a substrate in one embodiment.
[0057] These figures depict various embodiments of the present disclosure for illustrative purposes only. Numerous variations, configurations, and other embodiments will become apparent from the detailed discussion that follows. Additionally, it will be understood that the above figures are not necessarily drawn to scale, and are not intended to limit the described embodiments to the particular configurations shown. For example, while some figures generally depict straight lines, right angles, and smooth surfaces, given the practical limitations of manufacturing processes, actual implementations of the disclosed technology may have less than perfect straight lines and right angles, and some features may have surface topographies or otherwise not be smooth in their surfaces. In short, the above figures are provided merely to depict exemplary structures. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0058] overview Embodiments of the present disclosure include fabrics of nanofibers (and / or nanofiber yarns) further comprising an adhesive. In some embodiments, the nanofibers may be twisted or both twisted and coiled into nanofiber yarns prior to forming a fabric from the nanofibers and / or nanofiber yarns. In these embodiments, the twisting and / or coiling can facilitate stretching the nanofiber fabric to conform to the topography of the surface of the underlying substrate while maintaining their original position and orientation relative to one another (i.e., before being placed on and conforming to the surface of the substrate). Additionally, in some embodiments, an adhesive (or adhesive-free attachment technique such as a graphene sheet) may be selectively placed on or within some of the nanofibers of the nanofiber fabric. The adhesive (or other adhesive-free attachment) allows the nanofiber fabric to be attached to the underlying substrate. While allowing for the application of adhesive to the nanofibers of the nanofiber fabric, the selective location of the adhesive on the fabric limits the contact area between the adhesive and the nanofibers of the nanofiber fabric. The use of adhesive in this manner can help maintain beneficial properties of the nanofibers (e.g., thermal conductivity, electrical conductivity, infrared (IR) light transparency) that may otherwise be reduced by the more widespread presence of adhesive. Some embodiments described herein can be attached to one or more release liners to improve the convenience of storing, handling, and attaching the nanofiber fabrics of the present disclosure to substrates.
[0059] The embodiments described herein contrast with many existing nanofiber yarn configurations, in which the nanofiber yarn is embedded in a polymer or completely coated with an adhesive. This is illustrated in FIG. 1, which shows the nanofiber embedded in an adhesive layer and on a polymer sheet. While this configuration allows for convenient attachment of the nanofiber yarn, the adhesive layer (and possibly the polymer sheet) can inhibit or otherwise reduce the advantageous properties of the carbon nanofiber. For example, embedding the nanofiber in an adhesive layer prevents (either partially or fully) the nanofiber from contacting the underlying substrate. Without good physical contact, the exceptional electrical and thermal conductivity of the nanofiber yarn is sequestered within the adhesive layer, thus making it less likely that the benefits of these properties will extend to the substrate (or entire assembly). Additionally, having an adhesive and / or polymer sheet coextensive with the nanofiber often reduces the transparency of the combined polymer sheet and nanofiber to some wavelengths of light (e.g., IR radiation).
[0060] Before describing the nanofiber fabric of the present disclosure, the nanofiber forest and nanofiber sheet will be described below.
[0061] Nanofiber Forest As used herein, the term "nanofiber" refers to fibers with a diameter of less than 1 μm. Although the embodiments herein are described as being primarily made from carbon nanotubes, it will be understood that other carbon allotropes, even graphene, micron- or nano-scale graphite fibers and / or graphite plates, and even nanoscale fibers of other compositions, such as boron nitride, can be densified using the techniques described below. As used herein, the terms "nanofiber" and "carbon nanotube" encompass both single-walled and / or multi-walled carbon nanotubes, in which the carbon atoms are linked together to form a cylindrical structure. In some embodiments, the carbon nanotubes referred to herein are 4-10 walls. As used herein, the term "nanofiber sheet" or simply "sheet" refers to a sheet of nanofibers in which the nanofibers have been oriented by a stretching process (described in PCT Publication No. WO2007 / 015710, incorporated herein in its entirety) such that the longitudinal axes of the nanofibers of the sheet are parallel to the major surfaces of the sheet, rather than perpendicular to the major surfaces of the sheet (i.e., the as-deposited morphology of the sheet, often referred to as a "forest"). These are illustrated and shown in Figures 3 and 4, respectively.
[0062] The dimensions of carbon nanotubes can vary greatly depending on the manufacturing method used. For example, carbon nanotubes can have diameters between 0.4 nm and 100 nm, and their lengths can range from 10 μm to over 55.5 cm. Carbon nanotubes also have very high aspect ratios (ratio of length to diameter) and can be as high as 132,000,000:1 or more. Given the wide range of possible dimensions, carbon nanotubes The properties of carbon nanotubes are highly adjustable, or "tunable." Although many intriguing properties of carbon nanotubes have been identified, harnessing their properties in practical applications requires scalable and controllable production methods that can preserve or enhance their properties.
[0063] Due to their unique structure, carbon nanotubes have specific mechanical, electrical, chemical, thermal and optical properties that make them highly suitable for certain applications. In particular, carbon nanotubes exhibit excellent electrical conductivity, high mechanical strength, good thermal stability and are also hydrophobic. In addition to these properties, carbon nanotubes may also exhibit useful optical properties. For example, carbon nanotubes can be used in light emitting diodes (LEDs) and photodetectors to emit or detect light of a narrow selection of wavelengths. Carbon nanotubes may also prove useful for photon and / or phonon transport.
[0064] According to various embodiments of the present disclosure, nanofibers (including, but not limited to, carbon nanotubes) can be arranged in a variety of configurations, including configurations referred to herein as "forests." As used herein, a "forest" of nanofibers or carbon nanotubes refers to oriented nanofibers having approximately equal dimensions arranged substantially parallel to one another on a substrate. FIG. 2 shows an example of a nanofiber forest on a substrate. While the substrate can be of any shape, in some embodiments, the substrate has a flat surface on which the forest is built. As shown in FIG. 2, the height and / or diameter of the nanofibers in the forest can be approximately equal. In some cases, the forest can be "as-deposited," which means that the nanotubes have formed on the substrate or, in other cases, may be transferred from the substrate to a secondary substrate for growth.
[0065] The nanofiber forests disclosed herein can be relatively dense. In particular, the density of the disclosed nanofiber forests can be at least 1 billion nanofibers / cm2. In some specific embodiments, the density of the nanofiber forests described herein can be between 10 billion nanofibers / cm2 and 30 billion nanofibers / cm2. In other examples, the density of the nanofiber forests described herein can be in the range of 90 billion nanofibers / cm2. The forests can include regions of high or low density, and certain regions can be devoid of nanofibers. The nanofibers within the forest can also exhibit connectivity between the fibers. For example, adjacent nanofibers within a nanofiber forest can be attracted to each other by van der Waals forces. In any case, the density of the nanofibers within the forest can be increased by applying the techniques described herein.
[0066] Methods for producing nanofiber forests are described, for example, in PCT Publication WO2007 / 015710, which is incorporated herein in its entirety.
[0067] A variety of methods can be used to produce a forest of nanofiber precursors. An example method, shown in a schematic diagram in FIG. 3, involves growing the nanofibers in a high temperature furnace. In some embodiments, a catalyst may be deposited on a substrate, placed in a reactor, and then exposed to a fuel compound that is fed into the reactor. The substrate can withstand temperatures in excess of 800° C. or 1000° C. and can be an inert material. The substrate can comprise stainless steel or aluminum disposed on an underlying silicon (Si) wafer, although other ceramic substrates (e.g., alumina, zirconia, SiO2, glass ceramics) can be used in place of the Si wafer. In examples where the nanofibers of the precursor forest are carbon nanotubes, a carbon-based compound such as acetylene can be used as the fuel compound. After being introduced into the reactor, the fuel compound(s) may begin to deposit on the catalyst or may collect by growing upward from the substrate to form a forest of nanofibers. The reactor may also include a gas inlet through which the fuel compound(s) and a carrier gas can be fed into the reactor, and a gas outlet through which the consumed fuel compound and carrier gas can be released from the reactor. Examples of carrier gases include hydrogen, argon, and helium. These gases, especially hydrogen, may be introduced into the reactor to promote the growth of the nanofiber forest. Additionally, dopants may be added to the gas stream to be incorporated into the nanofibers.
[0068] In the process used to produce a multi-layered nanofiber forest, one nanofiber forest is formed on a substrate, followed by the growth of a second nanofiber forest in contact with the first nanofiber forest. The multi-layered nanofiber forest can be formed in various and suitable ways, such as by forming a first nanofiber forest on a substrate, depositing a catalyst on the first nanofiber forest, and then introducing additional fuel compounds into the reactor to promote the growth of the second nanofiber forest from the catalyst disposed on the first nanofiber forest. Depending on the growth method applied, the type of catalyst, and the location of the catalyst, the second nanofiber layer may either grow on top of the first nanofiber layer, or grow directly on the substrate after reactivating the catalyst, e.g., with hydrogen gas, and thus grow below the first nanofiber layer. In either case, the second nanofiber forest can be oriented approximately end-to-end with the nanofibers of the first nanofiber forest, provided that there is a readily detectable interface between the first and second forests. The multi-layered nanofiber forest may include any number of forests. For example, a multi-layer precursor forest may include two, three, four, five, or more forests.
[0069] Nanofiber Sheet In addition to being arranged in a forest configuration, the nanofibers of interest may be arranged in a sheet configuration. As used herein, the terms "nanofiber sheet," "nanotube sheet," or simply "sheet" refer to an arrangement of nanofibers in which the nanofibers are oriented end-to-end in a plane. An example nanofiber sheet is illustrated in FIG. 4A with dimensional indications. In some embodiments, the length and / or width of the sheet is greater than 100 times the thickness of the sheet. In some embodiments, the length, width, or both are greater than 103, 106, or 109 times the average thickness of the sheet. The thickness of the nanofiber sheet may be, for example, about 5 nm to 30 μm, and the length and width may be any length and width suitable for the intended application. In some embodiments, the length of the nanofiber sheet may be 1 cm to 10 meters, and the width may be 1 cm to 1 meter. These lengths are provided for illustrative purposes only. The length and width of the nanofiber sheets are constrained by the configuration of the production equipment, and are not constrained by the physical or chemical properties of either the nanotubes, forests, or the nanofiber sheets. For example, in a continuous process, sheets of any length can be produced. These sheets may be wound into rolls as they are produced.
[0070] The axis along which the nanofibers are oriented end-to-end, as shown in Figure 4A, is referred to as the direction of nanofiber orientation. In some embodiments, the direction of nanofiber orientation may be continuous throughout the nanofiber sheet. It will be understood that the nanofibers are not necessarily perfectly parallel to one another, and the direction of nanofiber orientation is an average or general measure of the direction of nanofiber orientation.
[0071] Nanofiber sheets can be constructed using any suitable process capable of producing such sheets. In some exemplary embodiments, the nanofiber sheets can be drawn from a nanofiber forest. An example of a nanofiber sheet being drawn from a nanofiber forest is shown in FIG. 4B.
[0072] As shown in Figure 4B, the nanofibers can be drawn laterally from the forest and then oriented end-to-end to form a nanofiber sheet. In embodiments where the nanofiber sheet is drawn from a nanofiber forest, the dimensions of the forest can be controlled to form a nanofiber sheet having specific dimensions. For example, the width of the nanofiber sheet can be approximately equal to the width of the nanofiber forest from which the sheet was drawn. Additionally, the length of the sheet can be controlled, for example, by terminating the drawing process when a desired sheet length is reached.
[0073] Nanofiber sheets have many properties that can be utilized in a variety of applications. For example, nanofiber sheets can have tunable opacity, high mechanical strength and flexibility, thermal and electrical conductivity, and can also exhibit hydrophobicity. Given the high degree of orientation of the nanofibers within the sheet, nanofiber sheets can be made extremely thin. In some instances, the thickness of the nanofiber sheet is on the order of about 10 nm (measured within normal measurement tolerances), making it nearly two-dimensional. In other instances, the thickness of the nanofiber sheet can be as large as 200 nm or 300 nm. Thus, the nanofiber sheet can be attached to a component with minimal increase in its thickness.
[0074] Similar to nanofiber forests, the nanofibers in a nanofiber sheet can be functionalized by treatments that add chemical groups or elements to the surface of the nanofibers in the sheet, providing a different chemical activity than the nanofibers alone. Functionalization of the nanofiber sheet can be performed on nanofibers that have been previously functionalized or on nanofibers that have not been previously functionalized. Functionalization can be performed using any of the techniques described herein, including, but not limited to, CVD and various doping techniques.
[0075] Nanofiber sheets drawn from a nanofiber forest can be of high purity, and may be attributable to greater than 90%, greater than 95%, or greater than 99% by weight of the nanofiber sheet. Similarly, the nanofiber sheet can comprise greater than 90%, greater than 95%, greater than 99%, or greater than 99.9% carbon by weight.
[0076] Nanofiber Fabric with Selectively Placed Adhesive As indicated above, embodiments of the present disclosure include nanofiber fabrics. The nanofibers of the fabric may be twisted, coiled, false twisted, or any combination thereof, thus forming nanofiber yarns. Examples of nanofiber fabrics described herein are configured such that the fabric can be stretched over a surface having an underlying three-dimensional topography (generally referred to as a "substrate") while also maintaining the orientation and position of the nanofibers of the fabric relative to one another. Although some of the embodiments described herein refer to nanofiber yarns, it should be understood that untwisted and / or uncoiled nanofibers, ribbons, sheets, or bundles may be used in place of nanofiber yarns to form the nanofiber fabrics described herein, and that the reference to nanofiber yarns is merely for convenience of description. Additionally, the nanofiber fabrics described herein can be formed by weaving nanofibers together (e.g., having warp and weft yarns), Or, one type of plurality of nanofibers oriented in a first direction can be formed by disposing one type of plurality of nanofibers on only one side of a second type of plurality of nanofibers oriented in a second direction.
[0077] The nanofibers of the fabric further comprise an adhesive selectively disposed on and / or within the nanofibers of the fabric, the selectively disposed adhesive helping to maintain properties of the nanofibers that would otherwise be diminished by a more uniform application of adhesive on the nanofibers.
[0078] FIG. 5A shows an example of a nanofiber used in a fabric of the present disclosure, where the nanofiber is configured as a twisted and coiled nanofiber yarn. As can be seen in the SEM micrograph, the nanofibers can be twisted together to bundle individual nanofibers into a yarn. The coil can be formed, among other things, by, for example, "overtwisting" the yarn or by winding the twisted yarn around a mandrel. In either case, the twist and coil within the nanofiber yarn essentially packs the long yarn into a compact form. That is, a twisted and coiled yarn having a first length can be stretched to a second length greater than the first length by stretching and / or untwisting the yarn. Nanofiber yarns such as the nanofiber yarn shown in FIG. 5A can be woven into a fabric as shown in the schematic diagram of FIG. 5B. As shown in this figure, nanofiber yarns (weft yarns) oriented in a first direction are woven together with nanofiber yarns (warp yarns) oriented in a second direction at an angle θ relative to the first direction. This creates a two-dimensional array of nanofiber yarns, also referred to herein as a nanofiber fabric. In the example shown in FIG. 5B, the angle θ is about 90° (±5° or within normal manufacturing variations). It will be understood that the angle θ may be greater or less than 90° depending on the fabric type and weaving method, and is shown for convenience of illustration only. For example, the angle θ may be within any of the following ranges: 30° to 165°, 45° to 135°, 60° to 95°, and 60° to 165°. In various examples, the gap formed between the nanofiber yarns oriented in a first direction and the nanofiber yarns oriented in a second direction can be within any of the following ranges: 1 μm to 1 mm, 10 μm to 1 mm, 10 μm to 100 μm, 100 μm to 500 μm, 500 μm to 2 mm, 1 mm to 10 mm, or greater than 10 mm.
[0079] The nanofiber yarn fabric shown in FIG. 5B may be stretched over a substrate having a three-dimensional topography, as shown in FIG. 5C. As shown in this example, the nanofiber yarn fabric of FIG. 5B is stretched over a curved surface in FIG. 5C. As also shown in the schematic diagram of FIG. 5C, the orientation and position of the nanofiber yarns of the nanofiber fabric are unchanged relative to the unstretched nanofiber fabric shown in FIG. 5B. That is, the angle θ is the same or nearly the same (i.e., θ±5°, e.g., 90°±5°), and the spacing between adjacent weft yarns and adjacent warp yarns is nearly unchanged (±5°) compared to the unstretched state shown in FIG. 5B. This is because, as shown above, when a nanofiber yarn is stretched to follow the underlying topography, it can be stretched and / or untwisted without changing the orientation and position of the yarns relative to each other. In some instances, the nanofiber yarn fabric is compliant and conforms to the surface topography (whether on a flat or curved surface) up to 10 microns higher or lower than the surrounding areas of the surface.
[0080] The nanofiber yarn fabrics of the present disclosure have the additional advantage of having adhesive selectively applied to portions of the nanofiber yarns (or simply nanofibers), whether those portions are exterior portions or interior portions. As noted above, this Selective application is beneficial because it preserves many of the nanofiber properties that would otherwise be diminished by the presence of an adhesive. For example, by selectively applying an adhesive to some but not all of the nanofiber yarn and / or nanofiber fabric, the nanofiber fabric can establish physical, electrical, and thermal contact with the underlying substrate without an intervening polymer and / or adhesive layer. In this manner, the beneficial properties of the nanofiber fabric can be imparted to the underlying substrate without being diminished by the adhesive. In another example, the absence of adhesive on a significant portion of the nanofiber yarn and / or nanofiber fabric (e.g., more than 50% of the surface area of the nanofibers, nanofiber yarn, and / or fabric) allows the nanofiber fabric to adhere to the underlying substrate while maintaining IR transparency.
[0081] The following description and corresponding figures show various exemplary embodiments of selective placement of adhesive on a nanofiber yarn fabric. Figures 6A, 6B, and 6C show various projections of a first example nanofiber fabric 600.
[0082] Looking first at FIG. 6A and simultaneously at FIG. 6B (a cross-sectional view of FIG. 6A at the location shown in FIG. 6A), there is shown a nanofiber fabric 600 comprising nanofiber yarn 604, frame 608, and adhesive layer 612 on frame 608.
[0083] In this example, nanofiber fabric 600 comprises horizontal and vertical nanofiber yarns 604, similar to the nanofiber fabric shown in Figure 5B. As with the nanofiber fabric of Figure 5B, it will be understood that the nanofiber yarns 604 may be at any angle and / or in any orientation relative to one another to form nanofiber fabric 600, not just the orthogonal patterns shown in Figure 5B or Figure 6A. The vertical and horizontal orientation of nanofiber yarns 604 shown in Figure 6A (and the nanofiber yarns shown in the examples below) is merely for convenience of explanation.
[0084] Nanofiber fabric 600 is bonded to frame 608 via adhesive layer 612. Adhesive layer 612 is disposed only on the surface of the frame, and thus adhesive layer 612 is selectively disposed on nanofiber fabric 600 at peripheral locations of the nanofiber fabric that overlap with 612. This is shown in Figure 6B, which shows nanofiber yarn 604F oriented in a first direction (horizontally in the plan view of Figure 6A) contacting nanofiber yarns 604A-604E oriented in a second direction (vertically in the plan view of Figure 6A). Nanofiber yarn 604F intersects nanofiber yarns 604A and 604E at the periphery of fabric 600 and also overlaps frame 608. Because adhesive layer 612 is disposed on frame 608, it is at these locations where the adhesive layer is selectively disposed on nanofiber fabric 600 where fabric 600 and frame 608 overlap. It will be appreciated that in some cases, the ends of nanofiber yarns 604, which are simply the ends of the yarns and not the junctions between the first and second direction yarns, may overlap frame 608. These ends are in contact with the selectively applied adhesive layer 612 by virtue of this contact with adhesive layer 612. Within the periphery of nanofiber fabric 600 (defined by contact with adhesive layer 612 on frame 608) is the interior portion of nanofiber fabric 600 where no adhesive is present. The dimensions of adhesive layer 612 may be within any of the following dimensions: 1 μm to 1 mm, 10 μm to 1 mm, 10 μm to 100 μm, 100 μm to 500 μm, 500 μm to 2 mm, 1 mm to 10 mm, and greater than 10 mm.
[0085] The absence of adhesive on the inner portion of nanofiber fabric 600 means that direct physical, electrical, and thermal contact can be established between nanofiber fabric 600 and the underlying substrate, as discussed above. This is shown in Figure 6C. As shown in Figure 6C, frame 608 has been removed. Nanofiber fabric 600 is 6C. Nanofiber yarn 604 is attached to substrate 616 via adhesive 612 on the periphery of textile 600 to form assembly 614, thus leaving the interior of nanofiber textile 600 on substrate 616 free of adhesive or polymer. As discussed above, properties such as thermal and electrical conductivity and IR transparency of nanofiber textile 600 that would be compromised by the presence of adhesive or polymer are not impeded. Also shown in FIG. 6C is gap 620 between substrate 616 and nanofiber yarn 604F, the height of which corresponds to the diameter of nanofiber yarn 604.
[0086] 7A, 7B, and 7C show examples similar to FIGS. 6A, 6B, and 6C, except that adhesive is selectively applied to different locations.
[0087] 7A and simultaneously FIG. 7B (a cross-sectional view of FIG. 7A at the location shown), nanofiber fabric 700 comprises nanofiber yarns 704, frame 708, and selectively applied adhesive deposits 712. Nanofiber fabric 700 is similar to the fabrics described above in the context of FIG. 5B, as was nanofiber fabric 600.
[0088] Nanofiber textile 700 differs from nanofiber textile 600 in that it has adhesive deposits 712 disposed at the junctions between nanofiber yarns oriented in a first direction and nanofiber yarns oriented in a second direction. These deposits are identified in FIG. 7A as circles of intersection between horizontal and vertical yarns, and are labeled in FIG. 7B as 712A, 712B, 712C, 712D, and 712E. This selective placement of adhesive on nanofiber textile 700 increases the amount of adhesive surface area and the number of adhesive contact points between nanofiber textile 700 and the underlying substrate 716, as shown in FIG. 7C. As is evident from inspection of the figure, despite the increased number of adhesive deposits 712 and adhesive surface area, the majority of the nanofiber yarn surface area (e.g., greater than 50% of the nanofiber / nanofiber yarn surface area) as well as the spaces between nanofiber yarns 704 are free of adhesive. This provides many of the same advantages as discussed above in the context of nanofiber textile 600.
[0089] In some examples, the thickness of deposit 712 may be between 0.1 μm and 1 mm. In some examples, the thickness of deposit 712 may be between 1% and 1000% greater than the thickness of the adhesive layer over the portions of the nanofiber yarn that do not correspond to the joints. In some examples, the above dimensions (i.e., the adhesive thickness measured from the surface of the nanofiber yarn to the surface of deposit 712 exposed to the ambient atmosphere) may be within any of the following ranges: 1 μm to 1 mm, 10 μm to 1 mm, 10 μm to 100 μm, 100 μm to 500 μm, 500 μm to 2 mm, 1 mm to 10 mm, or greater than 10 mm.
[0090] One method for applying adhesive to the nanofiber fabric 700 begins with dissolving the adhesive in a solvent. This adhesive solvent solution may then be sprayed onto the nanofiber fabric 700 as an aerosol. The size of the adhesive deposit at the junction between the nanofiber yarns oriented in the first and second directions, and the extent to which the adhesive ends up being disposed on the surface of the nanofiber yarn, depend on various factors of the aerosol. These factors include, but are not limited to, the concentration of adhesive molecules in the solvent, the volatility of the solvent itself, and the pressure of the carrier gas used to apply the solution, among others. However, regardless of these factors, under the conditions described herein, the adhesive aerosol can be deposited primarily at the junctions shown in Figures 7A and 7B. In yet another example, portions of the nanofiber fabric 700 may be masked to prevent adhesive deposition.
[0091] 8A, 8B, and 8C show yet another example of selectively depositing adhesive onto a nanofiber fabric. As with the other examples presented above, FIG. 8A shows a first direction and a second direction. 8B and 8C , nanofiber yarns 804 are infiltrated with adhesive 802. In the nanofibers and / or nanofibers illustrated in FIG. 8B and FIG. 8C , the nanofiber yarns 804 are infiltrated with adhesive 802. In the nanofibers and / or nanofibers illustrated in FIG. 8B and FIG. 8C , the nanofiber yarns 804 are infiltrated with adhesive 802. Infiltration of materials including organic molecules such as adhesive 802 can occur by dissolving the adhesive in a solvent and applying the solution to the nanofibers. The solvent carries the adhesive (or other material) to the interior of the nanofiber yarns. The interior of the nanofibers and / or nanofiber yarns includes interstices and other gaps between the constituent nanofibers. The solvent is then removed (by heating, vacuum, evaporation, or a combination thereof) leaving adhesive 802 (or other molecules, particles, or materials) disposed within, and possibly on, the nanofiber yarn.
[0092] In some instances, the adhesive (or polymer) disposed on the surface of nanofiber yarn 804 can also be removed using negative pressure (i.e., vacuum) and / or a focused stream of high pressure gas (e.g., nitrogen, argon, air, or other compressed gas or mixture of gases). These techniques are described in further detail in U.S. Patent Application No. 16 / 051,586, which is incorporated herein by reference in its entirety and is included in Appendix 1. Removing the adhesive (or polymer) from the surface of yarn 804 in this manner results in an adhesive-free yarn surface, which allows for direct contact to be established between nanofiber textile 800 and the underlying substrate, as described above.
[0093] The adhesive can then be allowed to flow in a liquid, flowable state through or along the fibers. This can be done before or after subsequent removal of the carrier solvent, such as by application of a solvent, heating above the glass transition temperature of the adhesive (or polymer) molecules, or application of centrifugal force, such as by spinning. Allowing the adhesive within the nanofiber yarn 804 to flow can, in some instances, form adhesive fillets 806 between adjacent nanofiber yarns 804 that come into contact with one another. These are shown in Figures 8B and 8C as fillets 806A, 806B, 806C, 806D, and 806E. The thickness (the maximum distance between the facing surfaces of yarn 804F and 804A to 804E, 806A to 806E, 810A to 810E) may be within any of the following ranges, i.e., 10 nm to 100 nm, 10 nm to 500 nm, 50 nm to 200 nm, 100 nm to 500 nm, 1 μm to 1 mm, 10 μm to 1 mm, 10 μm to 100 μm, 100 μm to 500 μm, 500 μm to 2 mm, 1 mm to 10 mm, or more than 10 mm.
[0094] Nanofiber fabric 800 may then be removed from frame 808 and underlying substrate 816. Whether caused by subsequent application of a solvent, heat, or other mechanism, some of the adhesive disposed within nanofibers 804 may flow from the nanofibers to contact substrate 816. This flowed adhesive then forms fillets 810A, 810B, 810C, 810D, and 810E. Once attached to substrate 816, nanofiber fabric 800, adhesive 802, and fillets 806 and 810 may be referred to as assembly 818.
[0095] The adhesive in any of the above-described embodiments may include, but is not limited to, acrylic adhesives, pressure sensitive adhesives, heat activated adhesives, thermoplastic polymers, epoxide or network cured polymers, elastomeric polymers, and combinations thereof, among others. In some embodiments, sol-gel precursor materials may be used in place of traditional organic adhesives. Thus, these precursor materials are chemically inert and can be used to bond well to substrates (e.g., ceramic, glass, or glass-ceramic) that may not adhere well to traditional adhesives. The sol-gel precursor may also react in situ with a substrate (such as a sol-gel precursor) to form a bond with the substrate. Embodiments including sol-gel precursors are described in more detail below.
[0096] While many of the embodiments described above include a first plurality of nanofiber yarns oriented at an angle relative to a second plurality of nanofibers, this need not be the case. In one embodiment, the nanofiber fabric includes an array of parallel nanofiber yarns that include adhesive at the ends that overlap the support frame, similar to the embodiment shown in Figure 6A. In one embodiment, the nanofiber fabric includes an array of parallel nanofiber yarns that are infiltrated with adhesive, similar to the embodiment shown in Figure 8A.
[0097] Sol-gel Adhesive Embodiments Any of the above-mentioned embodiments may use a sol-gel precursor as a "glue" material selectively placed at the ends of the nanofiber yarns that overlap the frame (e.g., as shown in FIG. 6A) and at the junctions between the nanofiber yarns oriented in a first direction and the nanofiber yarns oriented in a second direction (e.g., as shown in FIG. 7A) and / or permeated into some or all of the portions of the nanofiber yarns (e.g., as shown in FIG. 8A). In one example, the sol-gel precursor is applied to the nanofiber fabric (also described above) in any of the above-mentioned configurations before attaching it to a substrate. The nanofiber fabric may optionally be placed on a release liner for shipping or storage. In any case, the sol-gel reaction product initiates the sol-gel reaction when attaching the nanofiber fabric to an adhesive substrate. In an example, the precursors include precursors that form silicon dioxide (SiO2), aluminum oxide (Al2O3), yttrium oxide, and zinc sulfide, among others, when reacted.
[0098] Ceramic adhesives used in this manner produce more durable bonds between the nanofiber yarns and between the nanofiber fabric and the substrate, thus maintaining the orientation and position of the yarns relative to one another at ambient temperatures or with or without solvents or oxidizing agents, which can be beneficial in high temperature applications where polymer adhesives may flow at temperatures near their glass transition temperatures or in environments where the polymer solvates or decomposes.
[0099] One example of a method using sol-gel as an adhesive (rather than a polymer- or oligomer-based adhesive) begins by dissolving the sol-gel precursor(s) in a solvent, e.g., an alcohol such as ethanol or butanol. The solution of sol-gel precursor and solvent is then applied to the nanofiber(s) and / or nanofiber yarn(s). As described above, the sol-gel precursor and solvent may in some cases deposit non-uniformly at the junctions of the nanofibers (and nanofiber yarns) and / or penetrate into the inter-fiber gaps defined by the individual nanofibers (or collections of nanofibers) of the nanofiber yarn. In any case, the method continues by attaching the combination of sol-gel precursor, solvent, and nanofiber (yarn) assembly to a substrate and drying the assembly on the substrate, thus evaporating the solvent and allowing the precursors to react. Once reacted, the precursors form a mechanical bond between the nanofiber yarn and the substrate, as described above. The dimensions of the reacted sol-gel precursors can be within any of the ranges described above.
[0100] In another example, the nanofiber (yarn) assembly can be made electrically insulating, which can be achieved by applying a ceramic sol-gel precursor(s) to some or all of the substrate (e.g., to the portion where the nanofiber fabric will contact the substrate), curing the precursor to form a ceramic, and then attaching the fabric.
[0101] Graphene Attachment Embodiments 9A, 9B, and 9C show some examples of using graphene sheets to bond nanofiber yarns to their underlying substrate. In these examples, a graphene sheet can be applied to a nanofiber yarn such that a center portion of the graphene sheet conforms to a portion of the outer surface of the nanofiber yarn and an opposite end of the graphene sheet can be bonded to the underlying substrate on the opposite side of the nanofiber yarn. Van der Waals forces can then create an attractive force between the graphene sheet and the underlying substrate, and thus act as a physical constraint for the adhesive-free nanofiber yarn.
[0102] 9A is a schematic diagram of a cross section (perpendicular to the length of the nanofiber) of one example of this scenario, which includes a substrate 904, a nanofiber 908, and a graphene sheet 912. As shown, the nanofiber 908 is disposed on a surface of the substrate 904. The graphene sheet 912 is shown as having three portions: (1) a central portion 912A, (2) first and second side portions 912B and 912B', and (3) first and second end portions 912C and 912C'. As shown, the central portion 912A is disposed on a surface of the nanofiber 908. The first and second end portions 912C and 912C' are in contact with the substrate 904. The first and second side portions 912B and 912B' are bonded to the central portion 912A with corresponding first and second end portions 912C and 912C'. In this manner, the nanofibers 908 can be bonded to the substrate 904 without the use of adhesives or sol-gel systems, as discussed above.
[0103] 9B and 9C (the latter being an enlarged view of a portion of FIG. 9B) show images of an example of the diagram presented in FIG. 9A. In these images, a nanofiber yarn 920 is shown disposed on the surface of a substrate 916. A central portion 924 of a graphene sheet is disposed on the nanofiber yarn 920, similar to the central portion 912A shown in FIG. 9A. Due to the extreme thinness of the graphene sheet (corresponding in this case to one or two atomic layers of carbon atoms), the central portion 924 of the graphene sheet(s) in this example follows the surface topography of the nanofiber, and as a result, is nearly indistinguishable from one another. The physical boundary between the central portion 924 of the graphene sheet(s) and the nanofiber is more easily discernible in FIG. 9C than in FIG. 9B. For the same reason, the edge 932 of the graphene sheet, which contacts the substrate 916 and serves as an "anchor" for the rest of the graphene sheet, is discernible primarily as a collection of surface irregularities in the images of FIGS. 9B and 9C. Side portions 928 connect center portion 924 to ends 932, thus allowing nanofibers 920 to be pinned, bonded, or otherwise secured to substrate 916 by the graphene sheet without the use of adhesives or sol-gel precursors.
[0104] In some examples, a method for using graphene to attach nanofibers (and / or nanofiber yarns) to a substrate begins by suspending graphene particles (typically one atomic layer of carbon thick, but in some cases can be up to 5 or 10 atomic layers thick) in a solvent. Examples of solvents include water, ethanol, and butanol, among others. This method is followed by spraying the suspension of graphene sheets and solvent onto the nanofibers via aerosol. Without wishing to be bound by theory, it is believed that capillary forces wick the graphene sheets onto the surface of the nanofiber yarn (as described and illustrated above), thus bonding the graphene sheets to the substrate. The graphene sheets can conform to at least a portion of the surface of the nanofiber sheet and bond to the underlying substrate. This has the effect of anchoring, attaching, or otherwise bonding the nanofiber (or nanofiber yarn) to the substrate.
[0105] Any of the preceding exemplary embodiments may be used in the following applications: The nanofiber fabric of the present disclosure can be adhered to the inside or outside of an enclosure to provide electromagnetic interference (EMI) shielding to components disposed within the enclosure. In some cases, the nanofiber fabric acts as a barrier to EMI in the gigahertz range as well as polarized and non-polarized EMI. In another example, embodiments of the present disclosure, including those conveniently attached with a release liner, can be used to establish or re-establish electrical contact in an open circuit. For example, a portion of the nanofiber fabric of the present disclosure, with nanofiber yarns oriented in different directions, can be adhered to a conductor on the opposite side of an opening in a circuit. The two-dimensional network of conductive nanofiber yarns can make physical and electrical contact with the conductor unhindered by an intervening insulating adhesive, thus closing the circuit. In this way, embodiments of the present disclosure can be used as a conductive "patch" to a circuit. In some examples, embodiments of the present disclosure can be used in an electrically resistive capacity, thus functioning as a heating element.
[0106] Any of the embodiments described herein may be initially placed on or between a release layer (or multiple release layers) to facilitate storage and subsequent attachment to a substrate. In some examples, the release liner may be a thin (i.e., less than 0.5 mm thick), flexible, and / or elastically or plastically deformable substrate (e.g., polyethylene, plastically deformable polydimethylsiloxane (PDMS), metal foil, thermoplastic polymer film, among others) with a weak adhesive or an adhesive comprising a low surface energy material between the adhesive and the nanofiber fabric of the present disclosure. In one example, a thermoplastic film may be heated to soften, and the nanofiber yarns and / or fabric may be partially embedded (e.g., less than half or less than a quarter of the thickness of the yarns and / or fabric) such that the yarns and / or fabric are temporarily fixed within the thermoplastic film upon cooling, but are still easily removed after the opposite surface of the nanofiber fabric is adhered to a substrate. In this manner, the embodiments described herein may be produced and stored indefinitely between release liner layers. If desired, one layer of the release liner may be removed to expose the adhesive selectively disposed on the nanofiber fabric. The nanofiber fabric and remaining deformable release layer may then be allowed to conform to a substrate (even a substrate having a three-dimensional topography) without disturbing the orientation and / or position of the nanofiber yarns relative to one another, as described above.
[0107] One convenient aspect of using a release liner is that long lengths of nanofiber fabric (e.g., 50 centimeters or more) can be wrapped around a spool, and because the release liner separates adjacent layers of nanofiber fabric and corresponding adhesive from one another, the nanofiber fabric can be stored, shipped, and used in a physically compact form (i.e., several meters of nanofiber fabric and release liner wrapped around a spool of centimeter-diameter) without disturbing the adhesive deposit.
[0108] Any of the embodiments described herein may include particles or flakes of material within or on the adhesive deposit. For example, silver nanoparticles, graphene flakes, carbon nanoparticles (e.g., fullerenes), inorganic fillers (e.g., micron-sized particles of silica or carbon) may also be mixed with, added to, or placed on the adhesive deposit and / or the adhesive-filled nanofiber yarns described herein. These particles may improve adhesion between the nanofiber fabric and the substrate, improve the mechanical properties of the adhesive bond between the nanofiber fabric and the substrate, improve the mechanical properties (e.g., adhesive strength) between the nanofiber yarns of the nanofiber fabric, and improve the electrical, physical, and / or thermal contact between the nanofiber fabric and the substrate, among other benefits.
[0109] In another example, a film of single-walled nanotubes can be used to adhere a nanofiber fabric to a substrate. Single-walled carbon nanotubes have strong van der Waals forces that can create or promote adhesion between surfaces in contact with opposing sides of the single-walled nanotube film. A plurality of single-walled nanotubes, ranging in thickness from 1 nm to 3 nm, can be suspended in a solution of surfactant and water. The suspension can then be filtered (or the water / surfactant solution can be otherwise removed) to create a film of nanotubes. The film of nanotubes can then be attached to a nanofiber fabric. The nanofiber fabric can be placed on a substrate, with the nanofiber film sandwiched between the nanofiber fabric and the substrate. The single-walled nanotube film is thus positioned to promote adhesion between the nanofiber fabric and the substrate.
[0110] Further considerations The above description of the embodiments of the present disclosure has been presented for purposes of illustration and is not intended to be exhaustive or to limit the scope of the claims to the precise form disclosed. Those skilled in the relevant art will recognize that many modifications and variations are possible in light of the above disclosure.
[0111] The language used herein is selected primarily for ease of reading and instructional purposes, and may not be selected to describe or limit the subject matter of the present invention. Therefore, the scope of the disclosure is intended to be limited not by this detailed description, but by the claims that will be submitted upon application based on this specification. Thus, the disclosure of the present embodiment is intended to illustrate, but not to limit, the scope of the invention, which is set forth in the following claims.
Claims
1. A substrate; a nanofiber yarn disposed on the substrate; a graphene sheet having a central portion, a first side and a second side on either side of the central portion, a first end bonded to the first side, and a second end bonded to the second side; A nanofiber assembly, wherein the central portion of the graphene sheet is in contact with a side of the nanofiber yarn opposite the substrate, and the first and second ends are in contact with the substrate.
2. 10. The nanofiber assembly of claim 1, a first array of a plurality of the nanofiber yarns oriented in a first direction; a second array of a plurality of the nanofiber yarns oriented in a second direction different from the first direction, the second array contacting the first array at a plurality of junctions; an adhesive deposit on at least a portion of the plurality of joints; The nanofiber assembly, wherein one of the first array and the second array maintains an orientation relative to the other when following a three-dimensional topography.
3. disposing a nanofiber yarn on a substrate; suspending the graphene sheets in a solvent to form a graphene suspension; applying the graphene suspension to the nanofiber yarn on the substrate such that at least one of the graphene sheets in the suspension attaches the nanofiber yarn to the substrate.
4. disposing a first plurality of nanofiber yarns oriented in a first direction in the form of an array of nanofiber yarns over a second plurality of nanofiber yarns oriented in a second direction different from the first direction in the form of an array of nanofiber yarns, wherein the first plurality of nanofiber yarns and the second plurality of nanofiber yarns are in contact at a plurality of junctions to form a nanofiber fabric; applying an adhesive to at least a portion of the plurality of joints; placing the nanofiber fabric in contact with a release liner; The method includes:
5. 5. The method of claim 4, further comprising conforming the nanofiber fabric and the release liner to a three-dimensional surface, wherein the release liner and the nanofiber fabric conform to the three-dimensional surface.
6. 6. The method of claim 5, wherein the nanofiber fabric conforms to features on the three-dimensional surface that are at least 10 μm in size.
7. 6. The method of claim 5, further comprising removing the release liner while leaving the nanofiber fabric on the three-dimensional surface.
8. 6. The method of claim 5, wherein the first plurality of nanofiber yarns and the second plurality of nanofiber yarns maintain their orientation relative to one another when conformed to the three-dimensional surface.
9. 6. The method of claim 5, further comprising establishing electrical contact using a nanofiber fabric between two electrically insulated conductors on the three-dimensional surface.
10. 5. The method of claim 4, wherein at least a portion of the first plurality of nanofiber yarns or the second plurality of nanofiber yarns are twisted and coiled nanofiber yarns.
11. 5. The method of claim 4, wherein applying the adhesive further comprises applying an aerosol of adhesive to the nanofiber fabric, the aerosol accumulating on at least a portion of the plurality of bonds.
12. Applying the adhesive impregnating the first plurality of nanofiber yarns and the second plurality of nanofiber yarns with the adhesive; forming an adhesive fillet on at least a portion of the plurality of joints; The method of claim 4 further comprising:
13. The method of claim 12 , wherein the adhesive comprises a sol-gel precursor.
14. The method of claim 13 , wherein the sol-gel precursor comprises an aluminum oxide precursor and a solvent.
15. The method of claim 13 , wherein the sol-gel precursor comprises an yttrium oxide precursor and a solvent.
16. The method of claim 13 , wherein the sol-gel precursor comprises a zinc sulfide precursor and a solvent.
17. 5. The method of claim 4, wherein placing the first plurality of nanofiber yarns oriented in the first direction over the second plurality of nanofiber yarns in the second direction different from the first direction further comprises interweaving the first plurality of nanofiber yarns with the second plurality of nanofiber yarns to form the nanofiber fabric.
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