Systems, methods and compositions for producing liquid repellent materials - Patents.com

Abstract

The system, method, and composition for producing a liquid repellent material includes a first support configured to support a spool of flexible substrate and a second support configured to support a plurality of compression rollers configured to apply a force to a segment of the flexible substrate extending from the roll. The segment is located in a zone between the compression rollers. In one embodiment, the system includes a plurality of gas directors, each one configured to direct a flow of gas at least partially around one of the compression rollers. The flow causes a drop in air pressure in the zone. The system also includes a precursor supply configured to expose the substrate to a precursor (e.g., a siloxane precursor) to produce a coated or protected material.

Description

[Technical field]

[0001] The present disclosure relates to systems, methods, and compositions for producing liquid repellent materials. [Background technology]

[0002] Conventional oil- and water-repellent coatings are composed of highly fluorinated or perfluorinated compounds, or compounds and polymers that contain at least 60 percent by weight fluorine as part of their chemical formula. These compounds have been found to be persistent and bioaccumulative in the environment, causing irreparable harm to aquatic life and human consumers.

[0003] While most hydrocarbon-based coatings are capable of repelling water with varying degrees of effectiveness, there are no known hydrocarbon-based coating formulations that repel oily stains such as mineral oil, edible oils (olive oil, butter, palm oil) and grease stains (hexane, heptane, octane).

[0004] In addition to the environmental impacts of fluorinated compounds, and the inability of others to obtain textiles that are repellent to both water-based and hydrocarbon-based liquids, there is a need for a method of coating conductive yarns, fibers or fabrics that maintain electrical conductivity, are mechanically robust, and can withstand multiple launderings.

[0005] Therefore, there is a need to develop coatings that can repel water, grease, and oil while containing less than 30 weight percent fluorine, or ideally no fluorine components at all. There is also a widespread need in the art for improved processes for producing such yarns, fibers, and fabrics that are both hydrophobic and oleophobic, including those that are compatible with conductive materials.

[0006] In addition, large-scale production of coatings by chemical vapor deposition is limited by the need to use batch processes and / or challenges in maintaining a vacuum in a continuous processing chamber. Therefore, there is also a need for improved vapor deposition systems and methods for the continuous production of coated substrates. Summary of the Invention [Means for solving the problem]

[0007] Thus, in one embodiment, the system includes a first treatment chamber for coating a flexible substrate (such as a thick thread, fiber, fabric, textile, metal foil or metallized plastic) to provide a liquid repellent material. In some embodiments, a liquid repellent coating is provided on the substrate under and / or over the conductive material to produce a conductive material, such as a conductive thick thread, fiber or fabric. Depending on the embodiment, the system includes a second treatment chamber for sealing the conductive material with a sealing material. Both continuous and discontinuous coatings are contemplated. In addition, the coating may or may not penetrate the substrate depending on the coating material and the substrate properties, such as porosity and wettability.

[0008] In another embodiment, a device is provided for printing encapsulated conductive material onto any flat or smooth substrate (e.g., the surface of plastic, paper, transparent conductive oxide or metal oxide, or the surface of a nonwoven, prewoven or knitted fabric) that includes a printhead for coating and encapsulating the substrate, such as a thread, fiber or fabric. In some embodiments, the conductive material is completely encapsulated, and in other embodiments, the conductive material is partially encapsulated.

[0009] In some embodiments, the first processing chamber includes one or more load lock chambers at the substrate inlet and / or substrate outlet of the first processing chamber. In other embodiments, the second processing chamber includes one or more load lock chambers at the substrate inlet and / or substrate outlet of the second processing chamber. In further embodiments, the system uses a series of load lock chambers with successively lower pressures at the processing chamber inlet. In yet further embodiments, the system uses a series of load lock chambers with successively increasing pressures at the processing chamber outlet. In another embodiment, the load lock chamber is a reduced pressure zone or reduced pressure space where a reduced pressure effect is created on the substrate during the production of the liquid repellent material.

[0010] In some embodiments, the material production system includes a first support configured to support a spool of flexible substrate and a second support configured to support a plurality of compression rollers configured to apply a force to a segment of the flexible substrate extending from a roll. The compression rollers are positioned and configured to compress the segment located within a space or zone between the compression rollers. The system also includes a plurality of gas directors, each one configured to direct a flow of gas at least partially around one of the compression rollers. The flow causes a drop in air pressure within the zone. Additionally, the system has a precursor supply configured to expose the substrate to a precursor to result in a coated or protected material. In some embodiments, the material production system also includes a co-reactant supply configured to expose the substance and the precursor to a co-reactant.

[0011] The above embodiments are merely illustrative. Other embodiments described herein are within the scope of the disclosed subject matter. [Brief description of the drawings]

[0012] To allow the features of the present disclosure to be understood, a detailed description may be given by referring to certain embodiments, some of which are shown in the accompanying drawings. However, it should be noted that the drawings show only certain embodiments, and therefore should not be considered as limiting the scope of the present disclosure, since the scope of the disclosed subject matter encompasses other embodiments as well. The drawings are not necessarily to scale, and generally, emphasis is placed on illustrating the features of certain embodiments. In the drawings, like numerals are used to denote like parts throughout the various views.

[0013] [Figure 1] FIG. 1 illustrates one embodiment of a system for coating a flexible substrate, such as a thick thread, fiber, or fabric, with a conductive and / or liquid repellent substance, according to one or more aspects described herein, where the substrate is disposed in one or more processing chambers during processing. [Diagram 2] FIG. 2 illustrates one embodiment of a system for coating a flexible substrate, such as a thick thread, fiber, or fabric, with a conductive and / or liquid repellent substance, according to one or more aspects described herein, in which the substrate is continuously fed into one or more processing chambers during processing. [Figure 3A] FIG. 3A illustrates a processing chamber according to one or more embodiments described herein. [Figure 3B] FIG. 3B shows further details of coating a substrate according to one or more embodiments described herein. [Figure 3C] FIG. 3C illustrates a technique for coating a substrate according to one or more embodiments described herein. [Figure 4] FIG. 4 illustrates a wash chamber according to one or more embodiments described herein. [Figure 5A] FIG. 5A illustrates an embodiment of a processing chamber in accordance with one or more aspects described herein. [Figure 5B] FIG. 5B illustrates an embodiment of a processing chamber according to one or more aspects described herein. [Figure 6A]FIG. 6A illustrates an embodiment of a print head for depositing conductive and / or liquid repellent materials onto a substrate, such as a flat or smooth plastic, paper, transparent conductive oxide or metal oxide surface, or a nonwoven, pre-woven or knitted fabric surface, according to one or more aspects described herein, where the substrate is printed or sprayed with a precursor of the conductive and / or liquid repellent material. [Figure 6B] FIG. 6B illustrates an embodiment of a print head for depositing conductive and / or liquid repellent materials onto a substrate, such as a flat or smooth plastic, paper, transparent conductive oxide or metal oxide surface, or a nonwoven, pre-woven or knitted fabric surface, according to one or more aspects described herein, where the substrate is printed or sprayed with a precursor of the conductive and / or liquid repellent material. [Figure 7A] FIG. 7A illustrates an embodiment of an entrance load lock chamber and an exit load lock chamber in accordance with one or more aspects described herein. [Figure 7B] FIG. 7B illustrates an embodiment of an entrance load lock chamber and an exit load lock chamber in accordance with one or more aspects described herein. [Figure 8(1)] FIG. 8 shows a scanning electron microscope image of one embodiment of a substrate coated with a liquid repellent material according to one or more aspects described herein. [Figure 8 (2)] FIG. 8 shows a scanning electron microscope image of one embodiment of a substrate coated with a liquid repellent material according to one or more aspects described herein. [Figure 8 (3)] FIG. 8 shows a scanning electron microscope image of one embodiment of a substrate coated with a liquid repellent material according to one or more aspects described herein. [Figure 9(1)] FIG. 9 shows a scanning electron microscope image of one embodiment of a substrate coated with a liquid repellent material according to one or more aspects described herein. [Figure 9 (2)] FIG. 9 shows a scanning electron microscope image of one embodiment of a substrate coated with a liquid repellent material according to one or more aspects described herein. [Figure 9 (3)]FIG. 9 shows a scanning electron microscope image of one embodiment of a substrate coated with a liquid repellent material according to one or more aspects described herein.

[0014] Corresponding reference characters indicate corresponding parts throughout the several views. The examples described herein illustrate some embodiments, but should not be construed as limiting the scope in any way. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present disclosure relates to methods and processes for making conductive, coated, protected, and / or liquid repellent materials, such as plastics, metallized plastics, metal foils, and textiles (e.g., fibers, yarns, and fabrics). In one embodiment, polysiloxane coatings are applied to a substrate via vapor deposition and condensation of siloxane monomers, dimers, trimers, or other oligomers.

[0016] Advantageously, in some embodiments, the methods and processes for preparing the liquid repellent coating are integrated with a high throughput process for producing conductive or liquid repellent materials, such as textiles, fibers, thick yarns, or fabrics resulting from the methods and processes. Further details regarding conductive fabrics and thick yarns can be found in PCT Publication No. WO2021194931A1 (Andrew, Baima, and Beach), U.S. Patent Application Publication No. 2019 / 0230745A1 (Andrew, Zhang, and Baima), published on July 25, 2019, and entitled "Electrically-heated fiber, fabric, or textile for heated apparel," and U.S. Patent Application Publication No. 2018 / 0269006A1 (Andrew and Zhang), published on September 20, 2018, and entitled "Polymeric capacitors for energy storage devices, method of manufacture thereof and articles comprising the same." Each of these documents is incorporated herein in its entirety.

[0017] Generally speaking, in one embodiment, a system is provided herein for continuously producing a protected and / or conductive material (such as a conductive thick thread, fiber, or fabric) by processing a flexible substrate, such as a raw or unprocessed thick thread, fiber, or fabric. The system includes a first, a second, and an optional third processing chamber and a spooling mechanism. For example, the first processing chamber is for coating the substrate with a conductive polymer material. The first processing chamber introduces a precursor (e.g., a monomer) and an initiator that form the conductive polymer material. The second processing chamber is for sealing the conductive material with a sealing insulating material. The first spooling mechanism stores the substrate in the first processing chamber and flows the substrate through the first processing chamber during coating. The second spooling mechanism receives the substrate such that the substrate flows continuously in a direction from the first processing chamber to the second processing chamber. The flow speeds of the first and second spooling mechanisms are selected to allow the substrate to be coated with a conductive material and sealed with a sealing material (e.g., siloxane). The substrate is then sealed and wound onto a spool to form a spool of conductive, liquid repellent, coated or protected material.

[0018] In one embodiment, the first and second processing chambers are combined into a single processing chamber. For example, the separation of coating and sealing is achieved through one or more of a space or physical barrier in the single processing chamber. In another embodiment, the processing chamber includes a vapor phase introduction of precursors and initiators. For example, the precursors and initiators start to react in the vapor phase, and the coating is conformally formed around the substrate as a molecular layer. In such a case, the forming process as a molecular layer preserves the flexibility of the substrate after coating. In different embodiments, the precursor composition may be 3,4-ethylenedioxythiophene, the conductive material composition may be p-doped poly(3,4-ethylenedioxythiophene), and the sealing material composition may be an acrylate and / or a siloxane.

[0019] In another aspect, a device for printing a pattern of encapsulating and / or conductive polymer onto any flat or smooth substrate (such as the surface of plastic, metal foil, metallized plastic (e.g., chip bag substrate), paper, transparent conductive oxide or metal oxide, or the surface of a nonwoven, pre-woven or knitted fabric, etc.) comprises at least one print head for heating at least one precursor and generating at least one vapor within a target zone. For example, the vapor comprises a precursor and an initiator, and the surface is coated with a pattern of conductive material and protected with an encapsulating material as it passes through the target zone of the print head.

[0020] In one embodiment, the at least one print head includes a first print head for coating the surface with the conductive substrate and a second print head for sealing the conductive substrate with a sealing material. In another embodiment, the at least one print head includes a single print head for coating the surface with the conductive substrate and sealing the conductive substrate with a sealing material. Further embodiments use thermal-based and / or light-based initiation for coating with the sealing material.

[0021] By way of example, the conductive material composition may include p-doped poly(3,4-ethylenedioxythiophene) and the encapsulating material may include poly(acrylate). In another embodiment, the system includes a portable unit, the system further including a battery and a movable material tank for storage. In a further embodiment, the system further includes an outlet for delivering the cleaning solution to the substrate.

[0022] FIG. 1 shows a system 100 for manufacturing conductive, coated and / or protected materials. According to this embodiment, the system 100 includes a coating chamber 110, an optional washing chamber 120, and a sealing chamber 130. The chambers 110, 120, and 130 can be connected in series by a conveyor or other transport means, or can be located separately. An exemplary approach for creating functional thick yarns for wearable energy storage in the system embodiment of FIG. 1 is as follows: Starting with well-known and mass-produced thick yarns such as cotton, chambers 110 and 120 are used to deposit an electrothermally responsive coating onto the threads of the thick yarn. This will convert the thick yarns into Joule heaters. This coating does not change the characteristic feel, weight, or mechanical / tensile properties of the thick yarns. Finally, these thick yarns are sealed with a water-repellent insulating coating using chamber 130 to create a durable heater.

[0023] In the embodiment of FIG. 1, a spool 101 of substrate is first placed into a coating chamber 110. To affect the electrothermal response, the substrate is coated with a persistently p-doped conductive polymer poly(3,4-ethylenedioxythiophene), PEDOT-Cl, using a vapor deposition chamber 110 whose design has been adapted from previous efforts on in situ vapor polymerization of 3,4-ethylenedioxythiophene (EDOT). The main components of this chamber are an electric furnace that uniformly delivers FeCl vapor to a sample stage located 3-10 inches (about 7.6 to about 25.4 cm) above the furnace, a 5- to 36-inch square plate (about 32.6 cm square). 2 ~Approx. 232cm 2The chamber includes a heated sample stage (1000 nm), a stainless steel tube for delivering EDOT vapor from outside the chamber, and an in situ quartz crystal microbalance (QCM) sensor for real-time monitoring of the flow rate of EDOT / FeCl3 and the thickness of the deposited PEDOT film. An electric heater can be included outside the chamber near the EDOT inlet to facilitate vaporization of EDOT. An additional inert gas, such as nitrogen or argon, can be introduced into the chamber through a second gas inlet to control the process pressure and deliver EDOT vapor. Oligomerization and polymerization in the gas phase of EDOT is expected to occur in the region where the monomer vapor flux intersects with the conical FeCl3 vapor plume, and the resulting oligomers, with relatively low kinetic energy, will coat any surface placed within this region. Process pressures of 100-1000 mTorr during deposition result in mean free paths on the order of millimeters for these reactive oligomers. These mean free paths correspond to the surface roughness of the woven fabric, so that the oligomers described herein can sample multiple sites before finally adhering to a particular surface, resulting in a conformal coating. In addition, heating the sample stage during deposition imparts lateral mobility along the substrate surface to the adsorbed oligomers, thus resulting in better surface conformality and PEDOT conductivity. Stage heating also promotes oligomer-oligomer coupling to form higher molecular weight polymers.

[0024] The thickness of the polymer film growing in the chamber is monitored in real time by a quartz crystal microbalance (QCM) sensor located near the sample stage. The total deposition rate and film thickness values ​​reported by the QCM sensor during vapor deposition result from both the polymer film and unreacted EDOT / FeCl3 deposited on the sensor surface. The thickest polymer films are obtained after rinsing when the flow rates of EDOT and FeCl3 are matched during deposition. Unreacted EDOT or FeCl3 remain trapped in the film when their flow rates are incompatible and are leached out of the film during rinsing, resulting in a coating thickness significantly lower than that measured by the QCM sensor during deposition. Taking this into account, a typical polymer growth rate is about 10-15 nm per minute of exposure to the reactive vapor cone for a substrate stage temperature of 80 °C.

[0025] The coated substrate is then transferred to a cleaning chamber 120. A post-deposition rinse in the cleaning chamber 120 completely removes residual FeCl3 trapped in the vapor-deposited polymer film, resulting in a metal-free PEDOT-Cl coated substrate (e.g., thick yarn). The post-deposition rinse contains a dilute aqueous solution (0.001-0.1 moles / liter) of an acid (either monobasic or dibasic acid) that further dopes the PEDOT film to improve the electrical conductivity of the resulting coated substrate (e.g., thick yarn and fabrics containing such thick yarn). After rinsing, hot air is blown onto the substrate (e.g., fabric) to dry the substrate.

[0026] Finally, still referring to FIG. 1, the cleaned and coated substrate is transferred to the sealing chamber 130. To seal the PEDOT-Cl coated substrate (e.g., thick yarn) with the coating, a second vapor deposition chamber 130 is used, whose design is adapted from previous efforts on in situ radical chain polymerization of acrylate monomers. In some embodiments, the liquid-repellent coating is produced by polymerization of siloxane monomers. The main components of this chamber include a shallow cylindrical stainless steel shell with small ports for gas ingress and egress, a heated filament (typically nichrome) that can be resistively heated to 150-400°C, and a liquid-cooled stage on which the substrate is placed. For polymer film growth, initiators and monomers are vaporized by heating and vacuum. Vapors are then flowed over the heated filament to decompose the initiator into reactive radicals. The radical species and monomers condense on any substrate on the cooled stage, and the polymerization reaction occurs. Films are typically grown at pressures between 0.1 and 500 mTorr, and the growth rate can be adjusted by varying the partial pressures of initiator and monomer, chamber pressure, and filament temperature. Typical polymer growth rates are 10 nm per minute of exposure to reactive vapors. This encapsulation process is relatively simple and rapid than previous PEDOT-Cl coating operations, and does not require post-deposition rinsing. In another embodiment, this process can also be accomplished using UV (ultraviolet) light (wavelength <400 nm) instead of a wire heated filament to initiate polymerization. In the photoinitiated case, the reaction area is flooded with UV light, typically through a quartz glass window located in the ceiling of the vacuum chamber. In this case, a heated filament array is not required, and a photoinitiator is used instead of a thermally activated initiator.

[0027] For both the coating and sealing steps, the coating thickness can vary from about 100-1000 nm. Highly uniform conformal coatings were formed on the array of substrate surfaces exposed to reactive vapors in both chambers without special pretreatment or fixation steps. However, pretreatment (e.g., plasma treatment) and / or fixation steps are also contemplated. Furthermore, the polymer film is uniformly (macroscopically) deposited on the surface while conformally (microscopically) wrapping the curved surface of each exposed fibril of the yarns that make up the substrate. The high conformality of the conductive coating is particularly evident in SEM images of PEDOT-Cl coated wool gauze, where the PEDOT-Cl film follows the contours of all exposed surface features of the substrate with high fidelity over multiple length scales. Cross-sectional SEM studies confirmed that the PEDOT and protective acrylate films are pure surface coatings and that the majority of the fibrils / yarns are not swollen or stained by the polymer. Regardless of surface chemistry, thread / yarn composition, and weave density, successful vapor coating was performed without any pretreatment steps. The polymer coating did not change the feel of any substrate as determined by touching the substrate with a bare hand before and after coating. Furthermore, the coating did not increase the substrate weight by more than 2%.

[0028] To increase the coating thickness and throughput, the total residence time in the deposition zone and the stage temperature are two variables that require evaluation. A serpentine loop design is used to increase the total residence time experienced by a unit length of thick yarn as it passes through the deposition zone in each of the two polymer deposition chambers. The stage temperature is more difficult since there is a two-dimensional distribution across the plate, but thermocouples are placed throughout the stage to compare the "local" temperature to the quality of the coating. The local temperature of the thick yarn and the corresponding area can be used to correlate the effects of temperature to better resolution. The chamber pressure can also be used to tightly control the coating uniformity while increasing the throughput rate. Increased (>300 mTorr) chamber pressure then leads to a shorter mean free path of the chemical species involved in polymer chain growth within the chamber, which in turn leads to greater surface coverage due to a higher frequency of surface-limited reactions and suppression of line-of-sight deposition events.

[0029] As a further illustration, in one embodiment, poly(3,4-ethylenedioxythiophene) films formed from gas phase polymerization using iron salts are advantageous. In one embodiment, the dopant is uniformly distributed throughout the p-doped PEDOT film. In one embodiment, poly(3,4-ethylenedioxythiophene) is 10 10 atoms / cm 3 ~10 20 atoms / cm 3 Dopant concentration and ±10 3 atoms / cm 3 The doped layer is uniformly doped with a concentration variation of .

[0030] 3,4-Ethylenedioxythiophene has the structure of formula (1). [ka]

[0031] Upon polymerization it has the structure of formula (2). [ka] In the formula, "n" is the number of repeat units.

[0032] In one embodiment, n (the number of repeating units) may be greater than 20, preferably greater than 30, and more preferably greater than 40. In one embodiment, n is 20 to 10,000, preferably 50 to 9000, and more preferably 100 to 8500.

[0033] The iron salt may be any salt that can be vaporized (either by boiling or sublimation) at the reaction temperature. The iron salt may be a divalent iron salt, a trivalent iron salt, or a combination thereof. Generally, it is preferred that the iron salt is a trivalent iron salt. Examples of salts are iron(III) chloride, iron(III) bromide, iron(III) acetylacetonate, iron(III) sulfate, iron(III) acetate, iron(III) p-toluenesulfonate, and the like, or combinations thereof.

[0034] The amount of 3,4-ethylenedioxythiophene vapor in the reactor is 20-80 volume percent, preferably 40-60 volume percent, based on the total volume of 3,4-ethylenedioxythiophene and iron salt vapor. The amount of iron salt in the reactor is 20-80 volume percent, preferably 40-60 volume percent, based on the total volume of 3,4-ethylenedioxythiophene and iron salt vapor. Other inert gases, such as nitrogen and argon, may be present in the reactor during the reaction.

[0035] The substrate on which the film is placed is an electrically insulating substrate. The conductive substrate is 1×10 11 The conductive base material has an electrical volume resistivity of 1×10 11The substrate may be in the form of a slab having a thickness of a few nanometers to a few micrometers (e.g., 10 nanometers to 1000 micrometers), a thin film or sheet, a woven or nonwoven fiber, a thick thread, a fabric, a gel, a pixel, a particle, etc. The substrate may have a smooth surface (e.g., no intentional texture) or may be textured.

[0036] The substrate may have a surface area of ​​a few square millimeters to several thousand square meters. In one embodiment, the surface of the substrate may have a surface area of ​​10 square nanometers to 1000 square meters, preferably 100 square nanometers to 100 square meters, preferably 1 square centimeter to 1 square meter.

[0037] In one embodiment, the electrically insulating substrate may include a ceramic substrate or a polymer substrate. Ceramic substrates include metal oxides, metal carbides, metal nitrides, metal borides, metal silicides, metal oxycarbides, metal oxynitrides, metal boronitides, metal carbonitrides, metal borocarbides, etc., or combinations thereof. Examples of ceramics that may be used as substrates include silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide, cerium oxide, cadmium oxide, titanium nitride, silicon nitride, aluminum nitride, titanium carbide, silicon carbide, titanium niobium carbide, stoichiometric silicon borides (SiBn, n=14, 15, 40, etc.) (e.g., silicon triboride, SiB3, silicon tetraboride, SiB4, silicon hexaboride, SiB6, etc.), etc., or combinations thereof.

[0038] Organic polymers that are electrically insulating may also be used as the substrate and may be selected from a wide variety of thermoplastic polymers, blends of thermoplastic polymers, thermosetting polymers, or blends of thermoplastic and thermosetting polymers. The organic polymer may be a polymer, copolymer, terpolymer, or a blend of combinations comprising at least one of the organic polymers described above. The organic polymer may be an oligomer, homopolymer, copolymer, block copolymer, alternating block copolymer, random polymer, random copolymer, random block copolymer, graft copolymer, star block copolymer, dendrimer, polyelectrolyte (polymer with some repeating groups containing electrolyte), polyampholyte (polyelectrolyte with both cationic and anionic repeating groups), ionomer, etc., or a combination comprising at least one of the organic polymers described above. The organic polymer has a number average molecular weight of more than 10,000 grams / mole, preferably more than 20,000 grams / mole, more preferably more than 50,000 grams / mole.

[0039] Examples of organic polymers are polyacetals, polyolefins, polyacrylics, polycarbonates, polystyrenes, polyesters, polyamides, polyamideimides, polyarylates, polyarylsulfones, polyethersulfones, polyphenylene sulfides, polyvinyl chlorides, polysulfones, polyimides, polyetherimides, polytetrafluoroethylenes, polyetherketones, polyetheretherketones, polyetherketoneketones, polybenzoxazoles, polyphthalides, polyanhydrides, polyvinylethers, polyvinylthioethers, polyvinylalcohols, polyvinylketones, polyvinylhalides, polyvinylnitriles, polyvinylesters, polysulfonates, polysulfides, polythioesters, polysulfones, polysulfonamides, polyureas, polyphosphazenes, polyethylene terephthalates, polybutylene terephthalates, polyurethanes, polytetrafluoroethylenes, perfluoroelastomers, fluorinated ethylene propylenes, perfluoroalkoxyethylenes, polychlorotrifluoroethylenes, polyvinylidene fluorides, polysiloxanes, and the like, or combinations thereof.

[0040] Examples of polyelectrolytes are polystyrene sulfonate, polyacrylic acid, pectin, carrageenan, alginate, carboxymethylcellulose, polyvinylpyrrolidone, and the like, or combinations thereof.

[0041] Examples of thermosetting polymers include epoxy polymers, unsaturated polyester polymers, polyimide polymers, bismaleimide polymers, bismaleimide triazine polymers, cyanate ester polymers, vinyl polymers, benzoxazine polymers, benzocyclobutene polymers, acrylics, alkyds, phenol-formaldehyde polymers, novolacs, resoles, melamine-formaldehyde polymers, urea-formaldehyde polymers, hydroxymethylfurans, isocyanates, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, unsaturated polyesterimides, and the like, or combinations thereof.

[0042] The polymers and / or ceramics may be in the form of films, fibers, single strands of fibers, woven and non-woven fibers, fabrics, slabs, etc., or combinations thereof. The fibers may be treated with a surface modifier (e.g., a silane coupling agent) to improve adhesion, if desired.

[0043] In addition to fibers, fabrics, yarns and textiles, the present technology may be used to coat and / or seal other substrates of interest for other applications. For example, exemplary substrates are flat sheets such as paper, foil, Tyvek, polymer sheets including those listed above, porous flat membranes such as CELGARD®, or cylindrical or curved objects such as monofilament NYLON® yarns, monofilament silk yarns, or monofilament fiberglass yarns.

[0044] Suitable substrates further include plastics, metallized plastics, and metal foils. Exemplary substrates include greater than 80%, 70%, 60%, 50%, or 40% metal by atomic composition. Expected thicknesses of the metal layer of exemplary metallized plastics (e.g., metallized plastics used in chip bags) include coatings of less than 100 nm of metal on the plastic substrate.

[0045] Optionally, the substrate is pretreated, for example by exposure to an inert gas plasma, to activate the surface and enhance bonding between the substrate and the deposited material.

[0046] In one embodiment, the repellent material is deposited on a substrate on which a conductive polymer has already been deposited. In another embodiment, the repellent material is deposited on a substrate on which no conductive polymer has been applied. In a further embodiment, the conductive polymer is deposited on the repellent material as described above. Optionally, the substrate on which the repellent polymer and conductive polymer have been applied is coated with another layer of the repellent material, for example, the conductive polymer is sandwiched between layers of repellent material. It should be understood that the coatings and layers disclosed herein do not have to be continuous and may or may not penetrate the substrate and any previously applied coating materials.

[0047] With regard to the liquid repellent material, in one embodiment, the liquid repellent material comprises a polysiloxane. Examples of polysiloxanes include alkylhalosiloxanes, such as those obtained from the condensation of chlorosilane, dichlorosilane, and / or trichlorosilane monomers with diols and / or water, as shown in Scheme 1. In some embodiments, the silane monomers and diols are vaporized and mixed during coating. Exemplary chlorosilanes include one, two, or three alkyl groups bonded to each silicon atom. In further examples, halosilanes such as bromosilane, iodosilane, and fluorosilane are used as monomers. Exemplary alkyl groups ("R") include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl, or more. It should be understood that the alkyl groups may be branched or unbranched. Exemplary silanes include two alkyl groups that are the same (e.g., dimethyldichlorosilane, diethyldichlorosilane, diisopropyldichlorosilane), and in other embodiments, the silanes include two alkyl groups that are different (e.g., n-propylmethyldichlorosilane). As shown in Scheme 1, the monomers may include dimers, trimers, tetramers, pentamers, hexamers, heptamers, octamers, and / or other oligomers of dihalosilanes (e.g., dichlorosilane).

[0048] Exemplary diols include alkyl diols having 1 to 8 carbon atoms, which may be linear or branched (e.g., dihydroxymethane, ethylene glycol, propylene glycol, etc.), as shown in Scheme 1. Examples of diols also include polyethylene glycols having 1 to 8 ethylene units. Use of polypropylene glycol is also contemplated. [ka]

[0049] In some examples, the ratio of silane monomer to water and / or diol by volume is about 1:10, about 1:9, about 1:8, about 1:7, about 1:6, about 1:5, about 1:4, about 1:3, about 1:2, about 1:1, or about 1:0.5.

[0050] The silane monomer reacts with water and / or diol in one of the chambers disclosed herein (e.g., 110, 130, 210, 230, 410, 630A, 630B, 300A, 300B). In some embodiments, the formulation comprises a disiloxane or trisiloxane monomer that vaporizes during coating and is mixed with aryl ketone or diaryl ketone photoinitiator vapor and ultraviolet light of any wavelength less than 400 nm during coating. In other embodiments, the formulation comprises a disiloxane or trisiloxane monomer that vaporizes during coating and is mixed with diol, glycol and / or water vapor in the presence of an electrically generated reactive ion plasma, such as an argon ion plasma, during coating. In all embodiments, a vacuum chamber with multiple ports should be used to mix the silane or siloxane monomer and co-reactant vapors, thus inducing a reaction between them, to form a polymer coating directly on the surface of any desired substrate. Substrates can include paper, yarns, fibers, and textiles that are woven, knitted, or nonwoven, plastics (e.g., polyethylene terephthalate (PET), polylactic acid (PLA), and polyethylene naphthalate (PEN), or any of the polymers disclosed herein, and mixtures thereof), metallized plastics, and other composite materials. The reaction time is defined as the total time that the monomer and various co-reactant vapors are mixed in the treatment chamber to control the thickness of the polysiloxane coating formed on the substrate surface. Exemplary reaction times include 1 minute, 2 minutes, 5 minutes, 7.5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, or 120 minutes.

[0051] Polysiloxane coating thicknesses of less than 100 micrometers result in liquid repellent textiles and thick yarns. The relative ratio of siloxane monomer vapor to co-reactant vapor can be controlled to increase or decrease the degree of polycondensation between polymer chains, i.e., crosslink density, and increase or decrease the average polymer molecular weight of the polysiloxane coating. Crosslink density and polymer molecular weight can also be increased by introducing optional ultraviolet light or electrically generated reactive ion plasma into the treatment chamber at the same time that the monomer vapor and co-reactant vapor are introduced into the chamber.

[0052] Further with regard to the liquid repellent material, in one embodiment, the liquid repellent material comprises a poly(acrylate). In one embodiment, a method of coating a substrate with a liquid repellent polymer comprises vaporizing an acrylate, vaporizing a diacrylate, vaporizing an initiator, and initiating polymerization of the acrylate and diacrylate on the substrate.

[0053] Exemplary acrylates include fluoroalkyl acrylates such as 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl acrylate, and siloxyalkyl acrylates such as 3-[tris(trimethylsiloxy)silyl]propyl methacrylate. In one embodiment, the acrylate includes 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate.

[0054] Exemplary diacrylates include alkyl diol diacrylates such as 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol diacrylate, hi one embodiment, the diacrylate includes 1,4-butanediol diacrylate.

[0055] The polymerization may be initiated by heat and / or light, hi one embodiment, the initiator comprises a photoinitiator, such as 2-hydroxy-2-methylpropiophenone.

[0056] FIG. 2 shows a system 200 for producing 230 protective and / or conductive 210 material that is rinsed in acid and sealed with 220 protective coating, where the material is continuously fed during processing. The coating chambers 210, 220, and 230 are designed to maintain an appropriate vacuum despite the inlet of the substrate and the outlet of the protected material. In the embodiment of FIG. 2, the substrate is first passed through the coating chamber 210. The substrate is then continuously fed into the cleaning chamber 220. The substrate is then continuously fed into the sealing chamber 230.

[0057] In one example, the vacuum can be maintained using self-induced friction amplification, where pulling on the substrate in a given direction causes the opening to pinch tighter on the substrate, creating a seal. A well-known example of this type of sealing is the familiar finger trap toy or towing stock device. In another example, an external vacuum housing, similar to a glove box, can be implemented to maintain the vacuum while feeding the substrate into the deposition chamber.

[0058] In yet another example, for example in large scale factory production, a single chamber could be used that contains all of the functions of the three chambers 210, 220, 230.

[0059] Figures 3A-3C depict further details of a coating chamber 410, such as chamber 110 (Figure 1) or chamber 210 (Figure 2). In the embodiment of Figure 3A, the substrate 302 enters the top of the chamber and contacts a heated substrate stage 304 positioned above a port that introduces monomer precursors for coating. A vacuum of 0.3-1.0 Torr is maintained using the techniques discussed above, and a QCM sensor 306 monitors the process.

[0060] In the embodiment of Figure 3B, the monomer delivery process is shown in further detail. The EDOT delivery ampoule 310 is transported using inert gas delivered from inlet 312 to a heated vaporizer 314. Additional components including safety shutoff 415 and liquid flow controller 316 are used to ensure that an appropriate flow rate is maintained so that the material may be coated as the thick yarn is delivered by the spooling mechanism described above.

[0061] In the embodiment of FIG. 3C, a serpentine stage 419 is shown designed to coat the thick yarn 320. The serpentine stage 419 includes a base 322 and a number of rotating guides 324 spaced along the left and right sides of the base 322. When the serpentine stage 419 is positioned in the chamber 410, the thick yarn 320 snakes back and forth through the rotating guides 324 as it is wound onto the spool, ensuring uniform coating and increased residence time. In one embodiment, a separate serpentine stage is used in each of the processing chambers, i.e., the coating chamber and the sealing processing chamber, and the speed of spool winding is matched and selected such that the coating and sealing processes result in a uniformly sealed and coated thick yarn as the thick yarn 320 enters the serpentine stage 419 at position 326 and exits the serpentine stage at position 328. Applicant has found that the combination of a serpentine stage with vapor deposition advantageously results in a uniform coating.

[0062] FIG. 4 shows further details of the cleaning chamber 520, which may be used as the cleaning chamber 120 (FIG. 1) or 220 (FIG. 2). To remove excess oxidant and obtain a stably doped conductive polymer, the substrate is rinsed using a monoprotic acid, such as 0.1 mole / liter hydrochloric acid (HCl), delivered from a source 420, entering through a port 424 and exiting through a port 426. As depicted in FIG. 4, the acid can be sprayed through the textile or thick yarn via the source 420. The textile or thick yarn can be fed through a set of squeegee rollers 428 and then dried by blowing hot air through the textile or thick yarn from a dryer 422. The cleaning step does not need to be performed under vacuum, and therefore can be used without a vacuum in separate chamber embodiments of the overall system. In an integrated embodiment where coating, cleaning, and sealing are all performed in a single chamber, the cleaning process can also proceed under vacuum, with adjustments to how the rinse liquid is removed via an outlet 430.

[0063] 5A and 5B show further details of chamber 630A, which may be used interchangeably with any of the chambers described above, such as chamber 130 (FIG. 1) or 230 (FIG. 2). In the thermal initiation embodiment of FIG. 5A, monomer and initiator are fed into chamber 630B via inlet 530 and heated by heated filament array 420, which includes metal structure 421 that distributes heat 535 (which is depicted exaggeratedly as a mist of particles) for gas phase polymerization. Thick yarn enters at input 532 and exits at output 538, where it is coated in the manner described above. In one embodiment, a quartz crystal microbalance (QCM) sensor 534 is used to determine that the correct thickness has been achieved.

[0064] In the embodiment of FIG. 5B, instead of heating the monomer and initiator, a UV lamp 540 is placed at the top of chamber 630B, and UV light (wavelength <400 nm) 544 shines through a window 542 at the top of chamber 630B to interact with the monomer and initiator 546 for gas phase polymerization.

[0065] FIG. 6A shows a print head 300A for generating conductive patterns on any substrate 612, such as flat or smooth plastic, paper, transparent conductive oxide or metal oxide surfaces, or nonwoven, prewoven or knitted fabric surfaces, where a vapor of EDOT monomer and a solid oxidant, such as Fe(III) salt or copper(II) salt, is sprayed to form PEDOT directly on the surface. The print head 300A includes an initiator inlet 602 and a monomer inlet 604 for the oxidant and monomer described above, or any other variant disclosed herein, as well as a carrier gas inlet 606 and a manifold 608 that distributes gases to the interior of the print head, where polymerization 610 begins prior to deposition on the substrate 612. This print head can print intricately patterned conductive polymer lines and shapes, i.e. hand shapes, and can print with a resolution as small as ten microns (10 μm). The body of the print head is cylindrical in shape. The body is made of alumina or another thermally stable ceramic with a resistively heated filament 620 such as tungsten and a feedthrough for a thermocouple to control power delivery and maintain temperature. The heated filament coils within the body of the print head and heats the bottom, sidewalls, and tip of the funnel that delivers the oxidizer. The EDOT monomer is held within a reservoir that can feature a carrier gas line to help deliver the EDOT vapor to the substrate. The oxidizer is contained within a reservoir above the funnel section of the ceramic body and can incorporate an auger screw to control the delivery of the oxidizer to the heated funnel section that leads to the substrate. The hottest part of the funnel section is near the tip, which is achieved by having more wraps of the heated filament near the tip. The resistively heated filament heats the ceramic body, vaporizing the EDOT monomer and sublimating the oxidizer. The two vapors then flow out and down, where they interact above the surface, coating the surface with PEDOT. The height between the surface of the substrate and the tip of the print head can be 0.1-1.0 mm.

[0066] In the embodiment of FIG. 6A, the system 300A is a thermally initiated print head for printing encapsulating polymers onto any substrate, for example, flat or smooth plastic, paper, transparent conductive oxide or metal oxide surfaces, or nonwoven, prewoven or knitted fabric surfaces. The print head is, for example, an inkjet printer head less than 10 cm wide and located at a distance of about 1-10 mm from the substrate surface. The printer head comprises a nitrogen gas jet, a monomer supply, and an initiator supply. Nitrogen gas is used to help carry the monomer and initiator vapors out of their ampoules, and the monomer and initiator ampoules can have a configuration similar to that of FIG. 3B. The nitrogen gas jet creates a vacuum space so that the chemical reaction takes place in a localized vacuum region on the substrate. The monomer and initiator vapors are mixed and flowed into this localized vacuum region before flowing through the nichrome filament. This is because the presence of oxygen inhibits polymerization. The vaporized monomer / initiator mixture flows through a resistively heated nichrome filament that is heated at 150-400°C before reaching the substrate to initiate radicals that then radicalize the monomer, thereby polymerizing the encapsulant material on the substrate surface. The openings for the monomer / initiator are, for example, in the range of 10-100 micrometers in diameter in one embodiment.

[0067] With respect to the printhead embodiments described above, conventional printheads are known to print using liquid ink. For example, conventional inkjet printers propel liquid ink onto paper using either heat, pressure, or a combination thereof to generate patterns in a conventional manner well understood and known to those skilled in the art. However, conventional printheads are unable to deliver two components that are likely to react, and further lack the concept of having an initiating means, such as heat or light, to cause a reaction or the like. Conventional printheads are designed only for speed and printing on flat paper, have no provision for initiating chemical reactions, and therefore cannot be used to create conductive polymer coatings as described herein. Those skilled in the art will appreciate that conventional inkjet printers include both one or more printheads and a control mechanism that allows the printhead, which may include multiple output nozzles for different color inks, to move back and forth along a sheet of paper to print the required pattern. Such a control mechanism may be used with the present technique such that the innovative printhead described herein may move back and forth over any of the types of substrates described herein to form conductive and sealed coatings on those substrates.

[0068] Advantageously, the vapor deposition print head of the present disclosure includes a photo- or thermally initiated polymerization of a monomer and an initiator so that a conductive material such as PEDOT can be conformally deposited on a substrate such as a thread, fiber, fabric or textile. The print head can also include another nozzle through which the encapsulating material is delivered. A control mechanism can then time the delivery of the material so that as the print head moves over the substrate, a fully encapsulated conductive polymer such as PEDOT is delivered to the substrate in whatever pattern is desired. Because the vapor polymerization can occur within a short distance, such as a few centimeters, the result is a substrate that is conformally coated and encapsulated with the conductive polymer.

[0069] In the embodiment of FIG. 6B, system 300B is light initiated. The print head of system 300B functions similarly to 300A (see common reference numbers above), but instead of using a heated nichrome wire of filament 620 to generate radicals, the print head of system 300B generates radicals using UV light (wavelength < 400 nm) introduced from UV lamp 540 through window 542. In this case, nichrome filament 620 is not required. UV light will be applied to the space where the monomer and initiator vapors travel, the distance between the tip of the print head and the substrate, and the substrate. The part of the print head facing the substrate is made of quartz glass to allow UV light (wavelength < 400 nm) to pass through.

[0070] In some embodiments, the processing chamber (e.g., 110, 130, 210, 230, 410, 630A, 630B) further includes an entry load lock chamber and / or an exit load lock chamber, as shown in Figures 7A and 7B. During operation, the load lock chamber is maintained at a pressure between the external ambient pressure (approximately 760 Torr) and the reduced pressure within the processing chamber (1-1,000 milliTorr). Three or more distinct pressure zones (ambient pressure zone 721, one or more intermediate pressures (also referred to as "load lock zones") 722 and 724, and vacuum zone 723) are maintained while the substrate is being unrolled (discharged) and fed into the processing chamber, and / or after the substrate is removed from the processing chamber (and in some embodiments, rerolled). Advantageously, the entrance load lock chamber and / or the exit load lock chamber allow for continuous roll-to-roll feeding of a single substrate sheet unwound from a bolt under vacuum into the processing chamber, and the associated reverse process in which the single substrate sheet is wound up on a bolt under ambient conditions as it exits the vacuum chamber.

[0071] One embodiment of the entry load lock chamber 700A is shown in FIG. 7A. The segments or rolls of substrate 70 may be located outside, inside, or partially inside and partially outside of the entry load lock chamber 700A. In one embodiment, the segments or rolls of substrate 70 are located outside the entry load lock chamber 700A to facilitate changing of rolls of substrate 70 while maintaining a vacuum within the entry load lock chamber 700A and in the connected processing chambers. An exemplary substrate is about 300 feet long and 5 feet wide.

[0072] In one embodiment, a spool 802 of substrate 70 is secured by a support or scaffolding 710. Substrate 70 enters vacuum region 723 through a load lock-vacuum interface, space, or zone 804 located therebetween by compression rollers 731 and 732 supported by a frame or support (not shown). Depending on the embodiment, compression rollers 731, 732 can be electromechanically powered drive rollers that rotate. In one embodiment, compression rollers 731 and 732 are configured to rotate freely. The system has multiple gas directors 741, 742 associated with compression rollers 731, 732, respectively. To allow or cause compression rollers 731, 732 to rotate while maintaining a vacuum in the vacuum region / processing chamber, each of gas directors 741, 742 outputs a jet of nitrogen gas that is flowed at high velocity across a gap between the associated roller and the edge of the vacuum region / processing chamber. In one embodiment, gas director 741 creates a gas flow that flows completely or partially around compression roller 731, and gas director 742 creates a gas flow that flows completely or partially around compression roller 732. Without wishing to be bound by any particular hypothesis, the gas flow creates a pressure reduction effect, such as the Bernoulli effect. In one embodiment, the Bernoulli effect is used to maintain an intermediate vacuum (about 760 Torr to about 1 Torr) between ambient pressure region 721 and vacuum region 723. In one embodiment, ultra-high nitrogen gas flows ("nitrogen knives") 741 and 742 push out ambient gas and maintain a pressure difference between the ambient and intermediate pressure regions. In one embodiment, nitrogen gas jets / knives 741 and 742 also apply pressure to rollers 731 and 732, increasing contact between the rollers and substrate 70 at load lock-vacuum interface 804.

[0073] One embodiment of the exit load lock chamber 700B is shown in FIG. 7B. The substrate 70 exits the vacuum region 723 through a load lock-vacuum interface 804 between compression rollers 733 and 734, which are supported by a frame or support (not shown). Depending on the embodiment, the compression rollers 733 and 734 can be electromechanically powered drive rollers that rotate. In one embodiment, the compression rollers 733 and 734 are configured to rotate freely. Similar to the entrance load lock chamber 700A, the system has multiple gas directors 743 and 744 associated with the compression rollers 733 and 734, respectively. To allow or cause the compression rollers 733, 734 to rotate while maintaining a vacuum within the vacuum region / processing chamber, each of the gas directors 743, 744 outputs a jet of nitrogen gas that is flowed at high velocity across the gap between the associated roller and the edge of the vacuum region / processing chamber. This maintains an intermediate vacuum (about 760 Torr to about 1 Torr) between ambient pressure region 721 and vacuum region 723. In one embodiment, gas director 743 generates a flow of gas that flows completely or partially around compression roller 733, and gas director 744 generates a flow of gas that flows completely or partially around compression roller 734. In one embodiment, ultra-high nitrogen gas flows ("nitrogen knives") 743 and 744 push out the ambient gas and maintain a pressure differential between the ambient and intermediate pressure regions. In one embodiment, nitrogen gas jets / knives 743 and 744 also apply pressure to rollers 733 and 734, increasing contact between the rollers and substrate 70 at the load lock-vacuum interface.

[0074] Optionally, in some embodiments, the substrate 70 is wound on a spool 75, which may be located outside, inside, or partially inside and partially outside the exit load lock chamber 700B. In one embodiment, the roll of substrate 70 on spool 75 is located outside the entrance load lock chamber 700B to facilitate replacement of spool 75 while maintaining vacuum in the exit load lock chamber 700B and connected processing chambers. In one embodiment, the spool 75 is secured by a scaffolding 711.

[0075] In some embodiments, rollers 731, 732, 733, and 734 comprise silicone and separate the middle region from the vacuum region. Exemplary rollers are about 0.5 inches to about 1 inch (about 2.5 cm), about 1 inch (about 2.5 cm) to about 1.5 inches (about 3.8 cm), about 1.5 inches (about 3.8 cm) to about 2 inches (about 5.1 cm), about 2 inches (about 5.1 cm) to about 2.5 inches (about 6.4 cm), about 2.5 inches (about 6.4 cm) to about 3 inches (about 7.6 cm), about 3 inches (about 7.6 cm) to about 3.5 inches (about 8.9 cm), about 3.5 inches (about 8.9 cm) to about 4 inches (about 10.2 cm), about 4 inches (about 10.2 cm) to about 4.5 inches (about 11.4 cm), about 4.5 inches (about 11.4 cm) to about 5 inches (about 12.7 cm), about 5 inches (about 12.7 cm) to about 5.5 inches (about 14.0 cm). m), about 5.5 inches (about 14.0 cm) to about 6 inches (about 15.2 cm), about 6 inches (about 15.2 cm) to about 6.5 inches (about 16.5 cm), about 6.5 inches (about 16.5 cm) to about 7 inches (about 17.8 cm), about 7 inches (about 17.8 cm) to about 7.5 inches (about 19.1 cm), about 7.5 inches (about 19.1 cm) to about 8 inches (about 20.3 cm), about 8 inches (about 20.3 cm) to about 8.5 inches (about 21.6 cm), about 8.5 inches (about 21.6 cm) to about 9 inches (about 22.9 cm), about 9 inches (about 22.9 cm) to about 9.5 inches (about 24.1 cm), about 9.5 inches (about 24.1 cm) to about 10 inches (about 25.4 cm), or more in diameter.

[0076] In some embodiments, the vacuum region / processing chamber (e.g., 110, 130, 210, 230, 410, 630A, 630B) is connected to a mechanical pump that maintains the vacuum chamber at 1-1000 milliTorr (mTorr), and the silicone rollers allow this vacuum level to be maintained by preventing outgassing (bleed-through) from the intermediate region into the vacuum region. EXAMPLES

[0077] The following table provides exemplary embodiments of substrates coated with water- and / or oil-repellent materials produced using the systems and methods described herein. Water repellency was tested using ISO4920:2012 Textile fabrics - Determination of resistance to surface wetting (spray test). "Yes" corresponds to a coating that repels water for more than 8 hours. Oil repellency was measured using ISO14419:2010 Textiles - Oil repellency - Hydrocarbon resistance test, with ISO0 corresponding to no oil repellency and ISO8 corresponding to maximum oil repellency. In addition, the extremely good conformability of the coatings of sample numbers 20 and 21 is shown in the SEM images presented in Figures 8 and 9, respectively.

[0078] [Table 1(1)] [Table 1(2)] [Table 1(3)] [Table 1(4)]

[0079] Many examples of the utility of the present disclosure are contemplated by the inventors, including heated gloves, hats, and other garments, printed circuits embedded in garments to form wearable devices, etc. Various other applications of the present disclosure are envisioned, including wearables that provide heat to a user, monitor a user's health by measuring electrical signals and temperature, allow for the inclusion of other components such as blood pressure or oxygen sensors, etc.

[0080] Therefore, and as discussed and generally described above, various techniques are provided herein for coating conductive polymers onto substrates including flat or smooth plastic, paper, transparent conductive oxide or metal oxide surfaces, or nonwoven, prewoven or knitted fabric surfaces encapsulated with insulating material. The various components of Figures 1-6B can be rearranged or combined in different ways to construct a system for manufacturing materials. For example, any of chambers 110, 120, 130, 210, 220, 230, 410, 520, 630A, or 630B can be mixed and matched to provide a system according to the present disclosure. In addition, the process details discussed with respect to the chamber-based embodiments are also applicable to the printer / spray head embodiments 300A, 300B, and 300C. In addition, certain well-known details are only briefly touched upon, such as the use of an inert carrier gas to carry chemicals through the processing chamber, the use of a vacuum pump to maintain the vacuum, the use of a motor and other details of the spooling mechanism, as would be understood by one of ordinary skill in the art.

[0081] The fact that one or more specific embodiments for coating, cleaning and sealing are used to illustrate the concepts of the present technology is not meant to limit the present disclosure in any manner. Indeed, as stated above, the concepts disclosed herein are not limited to the disclosed substrates (e.g., textiles, thick yarns, fibers or fabrics). For example, many other applications of the different processes described herein are envisioned by the inventors and are included within the scope of the present disclosure. The presentation of a particular set of claims herein is not intended to limit the scope, but is made only to illustrate some of the exemplary embodiments encompassed by the present disclosure. For example, the techniques described herein may be scaled in size from large factory embodiments spanning many yards in each direction to smaller tabletop devices only a few feet in size. In addition to the fiber, fabric and thick yarn embodiments, the present disclosure may be used to generate circuits printed on any of the substrates identified above, and the coating and sealing process may be used to form the conductive lines of the circuits. By adding other electrical or semiconductor elements in ways known in the art, the final product is a wearable or non-wearable circuit or electronic device that can conform to any surface or configuration, offering significant advantages over the flat circuit boards currently used in the industry.

Claims

1. 1. A system for producing a liquid repellent material, comprising: a first load lock chamber including an inlet for the substrate and coupled to the inlet of the processing chamber; first and second rollers disposed at the entrance of the processing chamber between the first load lock chamber and the processing chamber; first and second inert gas outlets configured to flow inert gas along a length of a surface of each of the first and second rollers, respectively; Including, the system.

2. 10. The system of claim 1, further comprising a first spooling mechanism configured to store the substrate and positioned outside, inside, or partially outside and partially inside the load lock chamber, and to feed the substrate as it enters the processing chamber.

3. The method further includes the step of: third and fourth rollers disposed at the entrance of the processing chamber and between the processing chamber and the second load lock chamber; third and fourth inert gas outlets configured to flow inert gas over a length of a surface of each of the third and fourth rollers, respectively; and An outlet for the substrate The system of claim 1 , comprising:

4. The system of claim 3 , further comprising a second spooling mechanism configured to receive the substrate from the processing chamber and spool the substrate.

5. 1. A method for coating a substrate with a liquid repellent polymer, comprising the steps of: vaporizing the alkylhalosilane; vaporizing the water or the diol; condensing the alkylhalosilane and water or the alkylhalosilane and the diol on a substrate; A method comprising:

6. 6. The method of claim 5, wherein the alkyl group of the alkylhalosilane comprises a branched or unbranched methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, or octyl group.

7. The method of claim 5 or claim 6, wherein the alkylhalosilane comprises an alkylchlorosilane.

8. The method of claim 5 , wherein the water or the diol comprises water.

9. 9. The method of claim 8, further comprising the steps of vaporizing a diol and condensing the diol on the substrate with the alkylhalosilane.

10. The method of claim 5, wherein the water or the diol comprises a diol, the diol comprising from 1 to 8 carbon atoms.

11. The method of claim 5, wherein the water or the diol comprises a diol, the diol being an alkanol containing 1 to 8 carbon atoms.

12. The method of claim 5 , wherein the water or the diol comprises a diol, the diol comprising polyethylene glycol or polypropylene glycol.

13. 6. The method of claim 5, further comprising the steps of vaporizing a diaryl ketone photoinitiator and initiating the reaction by irradiating the process chamber with ultraviolet light.

14. 6. The method of claim 5, further comprising generating a reactive ion plasma in the processing chamber.

15. 1. A method for coating a substrate with a liquid repellent polymer, comprising the steps of: vaporizing the acrylate; vaporizing the diacrylate; vaporizing the initiator; initiating polymerization of the acrylate and the diacrylate on a substrate; A method comprising:

16. The method of claim 15 , wherein the acrylate comprises a fluoroalkyl acrylate.

17. The method of claim 16, wherein the acrylate comprises 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate.

18. The method of any one of claims 15 to 17, wherein the diacrylate comprises an alkyl diol diacrylate.

19. The method of claim 18, wherein the diacrylate comprises 1,4-butanediol diacrylate.

20. The method of any one of claims 15 to 19, wherein the initiator comprises 2-hydroxy-2-methylpropiophenone.

21. 21. The method of any one of claims 15 to 20, wherein initiating polymerization of the acrylate and the diacrylate comprises irradiating the substrate with ultraviolet light.

22. 20. The method of any one of claims 15 to 19, wherein initiating polymerization of the acrylate and the diacrylate comprises heating the substrate.

23. 1. A material manufacturing system comprising: a first support configured to support a spool of flexible substrate; a second support configured to support a plurality of compression rollers configured to apply a force to a segment of the flexible substrate extending from a roll, the segment being located within a zone between the compression rollers; a plurality of gas directors, each one of the gas directors configured to direct a flow of gas at least partially around one of the compression rollers, the flow causing a drop in air pressure within the zone; a precursor supply configured to expose the substrate to a precursor to produce a coated material; Including, the system.

Images