Oxidative chemical vapor deposition systems and methods for continuous deposition of substances on substrates

Abstract

Oxidative chemical vapor deposition systems and methods for continuous deposition of substances on substrates include a chamber, an actuator, and a power supply. The actuator is disposed within the chamber and configured to move a furnace from a first position to a second position. The power supply is configured to deliver power to the furnace. The system, in an embodiment has a dispenser. The dispenser has a reservoir coupled to a conduit and a fluidizing valve. The fluidizing valve controls the flow of a particulate solid from the reservoir through the conduit to an outlet disposed within the chamber, enabling continuous deposition of substances on substrates.

Description

PATENT Attorney Docket No.: 3122025 WO01 OXIDATIVE CHEMICAL VAPOR DEPOSITION SYSTEMS AND METHODS FOR CONTINUOUS DEPOSITION OF SUBSTANCES ON SUBSTRATES CROSS REFERENCE TO RELATED APPLICATION

[0001] This Application claims the benefit of U.S. Provisional Patent Application No.63 / 522,942, filed on June 23, 2023, which is incorporated by reference as if disclosed herein in its entirety. BACKGROUND

[0002] Wearable electronics have the potential to transform healthcare by enabling real-time and long-term monitoring. However, most conventional wearable technologies include rigid and / or bulky components that can cause discomfort. To overcome this limitation, one aim is to fabricate textile-based and / or textile-like wearable electronics including humidity sensors, temperature sensors, and thermoelectric generators. However, conventional textile-conductor hybrid materials have suffered from numerous disadvantages. For example, one challenge in the field has been to prepare materials that exhibit requisite electronic properties without causing skin irritation. Another challenge has been the preparation of materials that are gas permeable, e.g., cotton and silks coated in conductive polymers often lose breathability. Yet another challenge has been the preparation of materials that are not damaged when bent, stretched, exposed to humidity / moisture, and / or washed.

[0003] Moreover, conventional processes often use solution-based methods that generate large amounts of hazardous waste. Large-scale production using such techniques could cause substantial damage to the environment. Therefore there is a need to develop systems and methods for the manufacture of functionalized substrates that overcome these challenges.

[0004] One alternative to such solution-based methods is to use chemical vapor deposition. However, large-scale production of coatings by chemical vapor deposition have been limited by the need to use batch processes and / or challenges in maintaining a vacuum in continuous process chambers.

[0005] Additionally, conventional furnaces heat materials in a crucible and emit vapor in a cone having a higher flux near the center of the crucible that decreases as the angle from the center of the crucible increases. When the furnace and substrate are stationary, this results in an 1 29290897.1PATENT Attorney Docket No.: 3122025 WO01 uneven coating that is thicker near the center and thins out toward the circumference of the circle where the vapor cone intersects with the substrate. When the substrate is moved across the crucible, then this can lead to a thicker coating near the middle of the substrate and a thinner coating near the edges. This uneven coating limits the width of the substrate that can be coated. For example a stationary RADAK® furnace by Luxel Corporation can evenly coat a substrate about one foot in width. One option is to use a larger furnace. However such furnaces are large, heavy (about 100 kg without any solid), and costly. As the crucible size increases, the chance that rising vapor pressures in such crucibles will eject some solid / molten material increases.

[0006] Another limitation in continuous processes occurs when depletion of the material in the crucible requires that the process be stopped in order to refill the crucible. This is especially problematic for processes that employ a vacuum to enable / enhance vaporization of the material. In addition to stopping the process, the vacuum must be released, and then after the crucible is refilled, the chamber needs to be resealed and the air pumped out to reestablish the vacuum, which is time consuming. Elimination of such downtime would increase process efficiency.

[0007] Therefore, there is also a need for improved vapor deposition systems and methods for the continuous production of coated substrates. SUMMARY

[0008] Advantageously, the inventive subject matter comprises continuous oxidative chemical vapor deposition systems and methods for deposition of substances on substrates by providing dispensers that refill the crucibles of furnaces using a fluidizing valve that enables the vacuum to be maintained in the reaction chamber.

[0009] Additionally, or alternatively, mobile furnaces provide improved uniformity in deposition across the width of substrates having a variety of widths without the disadvantages of using larger furnaces discussed above. To further improve the uniformity of such coatings, in some embodiments, an in-line monomer delivery system is positioned near the furnace emission cone.

[0010] Therefore, in one embodiment, a system for coating a substrate comprises a chamber for oxidative chemical deposition of a substance on a flexible substrate (such as yarn, fiber, fabric, 2 29290897.1PATENT Attorney Docket No.: 3122025 WO01 a textile, metal foil or metalized plastic). In some embodiments, the substance is an electrically conductive polymer, producing electrically conductive materials.

[0011] In one embodiment, a first actuator is disposed within the chamber and configured to move a first furnace from a first position to a second position. In one embodiment, a power supply is configured to deliver power to the first furnace. Depending on the embodiment, the system comprises a second process chamber for encapsulating the electrically conductive material with an encapsulating substance. Both continuous and non-continuous coatings are contemplated. Additionally, coatings may penetrate into the substrate, or not, depending on the properties of the coating substance and substrate, e.g., porosity and wettability.

[0012] In one embodiment, the chamber comprises an inlet configured to continuously receive the substrate from a spool. In one embodiment, the chamber comprises an outlet configured to continuously discharge the substrate.

[0013] In one embodiment, the chamber is configured to maintain a pressure of about 0.1–1,000 millitorr, about 1–900 millitorr, about 100–800 millitorr, about 200–700 millitorr, about 250– 600 millitorr, or about 300–500 millitorr.

[0014] In one embodiment, the chamber further comprises a monomer inlet. In exemplary embodiments, the monomer inlet comprises a plurality of openings proximal to the first actuator between the first and second positions and configured to release monomer vapor.

[0015] In one embodiment, the first actuator is further configured to deliver power to the first furnace from the power supply. In one embodiment, the first actuator comprises a rotary rack and pinion actuator. In one embodiment, a second actuator is disposed within the chamber and configured to move a second furnace from a third position to a fourth position.

[0016] In one embodiment, a first dispenser comprises a first reservoir coupled to a first conduit and a first fluidizing valve, wherein the first fluidizing valve is configured to control a first flow of a particulate solid from the first reservoir through the first conduit to a first outlet disposed within the chamber. In some embodiments, the first actuator is further configured move the first furnace to a fifth position, wherein a first crucible of the first furnace is positioned to receive the particulate solid from the first outlet of the first dispenser. In some embodiments, the first dispenser further comprises a first valve between the first reservoir and 3 29290897.1PATENT Attorney Docket No.: 3122025 WO01 the first fluidizing valve. In further embodiments, the first dispenser further comprises a second valve between the first valve and the first fluidizing valve.

[0017] In one embodiment, a second dispenser comprises a second reservoir coupled to a second conduit and a second fluidizing valve, wherein the second fluidizing valve is configured to control a second flow of the particulate solid from the second reservoir through the second conduit to a second outlet disposed within the chamber. In some embodiments, the second actuator is further configured move the second furnace to a sixth position, wherein a second crucible of the second furnace is positioned to receive the particulate solid from the second outlet of the second dispenser. In some embodiments, the second dispenser further comprises a third valve between the second reservoir and the second fluidizing valve. In further embodiments, the second dispenser further comprises a fourth valve between the second valve and the second fluidizing valve.

[0018] In one embodiment, the volume of the reservoirs is the same as the volume of the furnace crucible, so the reservoir aliquots the amount of oxidant used to refill each crucible.

[0019] In one embodiment, a method of coating a substrate comprises: feeding the substrate into a chamber, exposing the substrate to a monomer, and vaporizing an oxidant in a first furnace and moving the first furnace from a first position to a second position by a first actuator disposed within the chamber.

[0020] In one embodiment, feeding the substrate into the chamber comprises unrolling the substrate from a spool. In one embodiment, the method further comprises discharging the substrate through an outlet in the chamber.

[0021] In one embodiment, the method further comprises reducing a pressure in the chamber to about 0.1–1,000 millitorr, about 1–900 millitorr, about 100–800 millitorr, about 200–700 millitorr, about 250–600 millitorr, or about 300–500 millitorr.

[0022] In one embodiment, exposing the substrate to a monomer comprises flowing monomer through a plurality of openings proximal to the first actuator between the first and second positions and configured to release monomer vapor. In one embodiment, wherein the monomer comprises 3,4-ethylenedioxythiophene.

[0023] In one embodiment, the first actuator delivers power from the power supply to the first furnace. 4 29290897.1PATENT Attorney Docket No.: 3122025 WO01

[0024] In one embodiment, the method further comprises vaporizing an oxidant in a second furnace and moving the second furnace from a third position to a fourth position by a second actuator disposed within the chamber.

[0025] In one embodiment, the first actuator moves the first furnace to a fifth position, such that a first crucible of the first furnace is positioned to receive the oxidant from a first dispenser having a first outlet disposed within the chamber.

[0026] In one embodiment, the method further comprises dispensing the oxidant from the first reservoir to the first crucible of the first furnace disposed within the chamber. In some embodiments, dispensing the oxidant comprises flowing, by a first fluidizing valve, at least a portion of the oxidant from the reservoir to the crucible. In one embodiment, the method further comprises closing a first valve between the first reservoir and the first fluidizing valve. In one embodiment, the method further comprises replacing or refilling the first reservoir with oxidant.

[0027] In one embodiment, the second actuator movies the second furnace to a sixth position, such that a second crucible of the second furnace is positioned to receive the oxidant from a second dispenser having a second outlet disposed within the chamber. In some embodiments, the method further comprises dispensing the oxidant from the second reservoir to a second crucible of the second furnace disposed within the chamber. In some embodiments dispensing the oxidant comprises flowing, by a second fluidizing valve. at least a portion of the oxidant from the reservoir to the crucible.

[0028] In one embodiment, the method further comprises closing a second valve between the second reservoir and the second fluidizing valve. In one embodiment, the method further comprises replacing or refilling the second reservoir with oxidant. In some embodiments, a volume of the first reservoir is about the same as the volume of the first crucible, and the volume of the second reservoir is about the same as the volume of the second crucible. In one embodiment, the oxidant comprises ferric chloride, FeCl3.

[0029] In some embodiments, the system comprises one or more load lock chambers at the substrate inlet and / or outlet of the chamber. In other embodiment, the system has a series of load lock chambers having successively lower pressures are used at the chamber inlet. In further embodiments, a series of load lock chambers having successively increasing pressures 5 29290897.1PATENT Attorney Docket No.: 3122025 WO01 are used at the chamber outlet. In yet further embodiments, each load lock chamber is a pressure reduction zone or space in which a pressure reduction effect is generated on the substrate during the production of the coating, e.g., conductive polymer or liquid repellant material(s).

[0030] In some embodiments, the methods further comprise coating the substrate in a liquid repellant material before and / or after the substrate is coated with electrically conductive polymer. Therefore, in one embodiment, a system comprises a process chamber for coating a flexible substrate (such as yarn, fiber, fabric, a textile, metal foil or metalized plastic), resulting in a liquid repellant substance. In some embodiments, liquid repellant coatings are applied on the substrate under and / or over an electrically conductive substance to produce an electrically conductive material, such as an electrically conductive yarn, fiber or fabric. Both continuous and non-continuous coatings are contemplated.

[0031] The above embodiments are exemplary only. Other embodiments as described herein are within the scope of the disclosed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] So that the manner in which the features of the disclosure can be understood, a detailed description may be had by reference to certain embodiments, some of which are illustrated in the accompanying drawings. It is to be noted, however, that the drawings illustrate only certain embodiments and are therefore not to be considered limiting of its scope, for the scope of the disclosed subject matter encompasses other embodiments as well. The drawings are not necessarily to scale, emphasis generally being placed upon illustrating the features of certain embodiments. In the drawings, like numerals are used to indicate like parts throughout the various views, in which:

[0033] FIGS.1A &1B illustrate an embodiment of a system for coating a flexible substrate with an electrically conductive substance, in which a substrate is continuously fed into a process chamber during processing, in accordance with one or more aspects set forth herein.

[0034] FIG.1C illustrates a cross section of an embodiment of a system for coating a flexible substrate with an electrically conductive substance, in which a substrate is continuously fed 6 29290897.1PATENT Attorney Docket No.: 3122025 WO01 into a process chamber during processing, in accordance with one or more aspects set forth herein.

[0035] FIGS.1D &1E illustrate an embodiment of a process chamber, in accordance with one or more aspects set forth herein.

[0036] FIG.1F illustrates a cross section of an embodiment of a process chamber, in accordance with one or more aspects set forth herein.

[0037] FIG.1G illustrates an embodiment of dispensers, in accordance with one or more aspects set forth herein.

[0038] FIG.1H illustrates a cross section of dispensers, in accordance with one or more aspects set forth herein.

[0039] FIG.1I illustrates embodiments of actuators, furnaces, and monomer inlets, in accordance with one or more aspects set forth herein.

[0040] FIG.1J illustrates an embodiment of an interface for power, thermocouple, monomer supply, and signals, in accordance with one or more aspects set forth herein.

[0041] FIG.1K illustrates embodiments of actuators, furnaces, and monomer inlets extending from a process chamber, in accordance with one or more aspects set forth herein.

[0042] FIG.1L illustrates an embodiment of an interface for power, thermocouple, monomer supply, and signals, in accordance with one or more aspects set forth herein.

[0043] FIGS.2A-D illustrate movement of a furnace by an actuator from a dispenser to one side of a substrate, across the width of the substrate, and to the opposite side of the substrate within a chamber, in accordance with one or more aspects set forth herein.

[0044] FIG.3 illustrates a technical drawing of an embodiment of a system for coating a flexible substrate with an electrically conductive substance, in which a substrate is continuously fed into a process chamber during processing, in accordance with one or more aspects set forth herein.

[0045] FIGS.4A-E illustrate an embodiment of a monomer delivery system, in accordance with one or more aspects set forth herein.

[0046] Corresponding reference characters indicate corresponding parts throughout several views. The examples set out herein illustrate several embodiments, but should not be construed as limiting in scope in any manner. 7 29290897.1PATENT Attorney Docket No.: 3122025 WO01 DETAILED DESCRIPTION

[0047] The present disclosure relates to continuous systems, methods, and processes for producing electrically conductive, coated, and / or protected materials. In some embodiments, high- throughput processes produce electrically conductive materials from textile substrates, including woven and non-woven materials, for example, fibers, yarns, fabrics, electrospun materials, paper, silk, and natural and synthetic cloths. In further embodiments, an electrode layer may be deposited on paper or other temperature sensitive substrates when combined with a suitable barrier material for applications in fuel cells, microelectromechanical systems, and other devices. Therefore, suitable substrates may further include, but are not limited to, fibrous substrates, such as papers and membranes. Exemplary substrates may further comprise metals (e.g., metal foils and metallized plastics), metal oxides, ceramics, glasses, silicon, and other device substrate materials. Plastic substrates may include, but are not limited to, polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polyethylene naphthalene (PEN), poly-styrene (PS), polycarbonates (PC), polyethylene (PE), poly-tetrafluoroethylene (PTFE), and others.

[0048] In one embodiment, a system for coating a substrate comprises a chamber for oxidative chemical deposition of a substance on any flexible substrate disclosed above. In some embodiments, the substance is an electrically conductive polymer, producing electrically conductive materials.

[0049] FIGS.1A–1L illustrate a system 100 for producing electrically conductive, coated and / or protected material. According to this embodiment, the system 100 includes a chamber 110. An exemplary approach to creating functional materials, e.g., for wearable energy storage, in the system embodiment of FIGS. 1A–1L is to: start with familiar and mass-produced textiles; deposit an electrothermally-responsive coating onto the textiles that will transform them into Joule heaters. This coating does not alter their characteristic feel, weight or mechanical / tensile properties of the textiles. The system may also comprise a cleaning chamber. The system can further comprise an encapsulating chamber that encapsulates the coated substrate with a coating (e.g., a water-repellant and / or insulating coating) to create durable conductors. The coating, cleaning, and encapsulating chambers can be serially linked by conveyors or other transport means or can be separately disposed. 8 29290897.1PATENT Attorney Docket No.: 3122025 WO01

[0050] In some aspects, the chamber comprises an inlet configured to continuously receive the substrate from a spool. In other aspects, the chamber comprises an outlet configured to continuously discharge the substrate, e.g., to another process or spool. In further aspects, the chamber is configured to maintain a pressure of about 0.1–1,000 millitorr, about 1–900 millitorr, about 100–800 millitorr, about 200–700 millitorr, about 250–600 millitorr, about 300–500 millitorr, about 500 millitorr to about 1 Torr, about 1–5 Torr, or about 5–10 Torr.

[0051] In the embodiment of FIGS.1A–1C, a substrate from spool (not shown) enters chamber 110 through one or more graduated pressure chambers 111. Additionally or alternatively, one or more load lock chambers may be used. Suitable load lock chambers include those described in PCT / US2022 / 049648 (Andrew, Kelliher, Cali, Monroe, Beach, and Nandy), filed November 11, 2022, and entitled “System, Method and Composition for Producing Liquid Repellant Materials.” Contemplated systems may comprises one or more graduated pressure chambers and / or load lock chambers at the substrate inlet and / or outlet of chambers that operate at sub- atmospheric pressure, inert environments, controlled-humidity environments, or other controlled conditions. In certain aspects, the system has a series of graduated pressure chambers and / or load lock chambers having successively lower pressures are used at the chamber inlet. In further aspects, a series of graduated pressure chambers and / or load lock chambers having successively increasing pressures are used at the chamber outlet. In yet further aspects, the graduated pressure chamber or load lock chamber is a pressure reduction zone or space in which a pressure reduction effect is generated on the substrate during the production of the coating, e.g., conductive polymer or liquid repellant material(s).

[0052] In an exemplary embodiment, the system 100 comprises two graduated pressure chambers 111 in series as shown in FIG.1A. Vacuum pumps 113, 114 and 116 remove gasses and create a vacuum in coating chamber 110 and one or more graduated pressure chambers 111, 112. Coating chamber 110 comprises an inner filter 115 with moving electrical furnaces 170 and a movable monomer delivery system 140 to deliver monomer vapors. Dispensers 190 are used to refill the crucible of furnace 170, e.g., with solid oxidant. In some embodiments, the substrate exits coating chamber 110 through one or more graduated pressure chambers and / or exit load lock chambers 112. In an exemplary embodiment, the system 100 comprises two 9 29290897.1PATENT Attorney Docket No.: 3122025 WO01 graduated pressure chambers 112 in series as shown in FIG.1A. Vacuum pumps may remove gasses from the one or more graduated pressure chambers and / or exit load lock chambers 112.

[0053] FIG.1B shows another view of the embodiment of system 100 shown in FIG.1A. From this perspective, interfaces 120 of chamber 110 are shown. In one embodiment, interface 120 comprises interface 121 for furnace power, thermocouple, and any further electrical connections and a handle as shown in FIG.1J and 1L. An exemplary path that substrate (not) may take through system 100 can be viewed in the cross section of system 100 shown in FIG.1C. In one embodiment, the substrate travels from left to right, although right to left is not excluded. The substrate travels through a series of openings in each chamber of system 100 and is guided by rollers within chamber 110. In some embodiments, filter 115 collects particles as the vapors travel from furnace 170, through the substrate, then through filter 115 before reaching pumps 116. Suitable filters have a hole spacing grid of about 60 by 60 squares per square inch. For example, filter 115 may comprise a stainless steel wire mesh having a wire diameter 0.0036 inches, and openings 0.0046 inches across as supplied by McMaster-Carr.

[0054] FIG.1D shows a perspective view of coating chamber 110, having door 119 positioned on the same side as interfaces 120. On operator loading substrate into the chamber will guide the leading edge of the substrate through the opening to coating chamber 110, around each guide roller and through opening 118. Top 117 provides access for maintenance, e.g., sweeping debris from the walls and floor of coating chamber 110. This view also shows opening 118 through which a substrate travels before entering the one or more graduated pressure chambers 112. Interfaces 120 provide access to three drawers—self-contained trays that each have a pair of moving electrical furnaces 170, which plug in-plug out. Linear actuators 180 are welded to their respective tray beds. Linear actuator 123, e.g., a vertical hydraulic linear actuator, allows for vertical motion of the monomer delivery system 140, e.g., piping grid.

[0055] FIG.1E shows a perspective view of another side of coating chamber 110. As in FIG.1D, substrate enters coating chamber 110 through opening 118. Closer views of oxidant loading systems 190 are also shown.

[0056] To affect an electrothermal response, a substrate is coated with the persistently p-doped conducting polymer poly(3,4-ethylenedioxythiophene), PEDOT-Cl, using a vapor deposition 10 29290897.1PATENT Attorney Docket No.: 3122025 WO01 chamber whose design was adapted from previous efforts on the in situ oxidative vapor phase polymerization of 3,4-ethylenedioxythiophene (EDOT).

[0057] By way of further explanation, in one embodiment, the poly(3,4-ethylenedioxythiophene) film formed from vapor phase polymerization using an iron salt is advantageous. In one embodiment, the dopant is uniformly distributed through the p-doped PEDOT film. In an embodiment, the poly(3,4-ethylenedioxythiophene) is uniformly doped having a dopant concentration of 1010atoms per cm3to 1020 atoms per cm3and a concentration variation of ±103atoms per cm3.

[0058] The 3,4-ethylenedioxythiophene has the structure of formula (1):

[0059] Upon polymerization,structure of formula (2):where “n” is the number of repeat units.

[0060] In an embodiment, n (the number of repeat units) may be greater than 20, preferably greater than 30, and more preferably greater than 40. In an embodiment, n is 20 to 10,000, preferably 50 to 9000, and more preferably 100 to 8500.

[0061] The iron salt may be any salt that can be vaporized (either by boiling or sublimation) at the reaction temperature. The iron salts may be divalent iron salts, trivalent iron salts, or a combination thereof. It is generally desirable for the iron salts to be trivalent iron salts. 11 29290897.1PATENT Attorney Docket No.: 3122025 WO01 Examples of salts are iron (III) chloride, iron (III) bromide, iron (III) acetylacetonate, iron (III) sulfate, iron (III) acetate, iron(III) p-toluenesulfonate, or the like, or a combination thereof.

[0062] The amount of the 3,4-ethylenedioxythiophene vapor in the reactor is 20 to 80 volume percent, preferably 40 to 60 volume percent relative to the volume of the sum of the vapors of 3,4-ethylenedioxythiophene and the iron-salt. The amount of iron salt in the reactor is 20 to 80 volume percent, preferably 40 to 60 volume percent relative to the volume of the sum of the vapors of 3,4-ethylenedioxythiophene and the iron-salt. Other inert gases such as nitrogen and argon may be present in the reactor during the reaction.

[0063] To vaporize the oxidant, in some aspects, a first actuator is disposed within the chamber and configured to move a first furnace from a first position to a second position. In other aspects, a second actuator is disposed within the chamber and configured to move a second furnace from a third position to a fourth position. It should be appreciated that one or more power supplies are configured to deliver power to the first and / or second furnace. For example, FIG.1F shows a cross-section of chamber 110 in which electrical furnaces 170 are configured to move perpendicular to the direction of substrate travel to uniformly deliver FeCl3 vapor to a substrate two to twelve inches above each furnace. Three furnaces 170 are shown, and three are omitted for clarity. In further aspects, actuators 180 are angled at angles less than or greater than 90° relative to the direction of substrate travel. Optional extra flanges provide flexibility to add electrical connections / ports.

[0064] FIG.1I illustrates one drawer / tray configured to slide out from one side of coating chamber 110 on track and rollers 125 (FIG.1K) by pulling handle 120. Two furnaces 120 and actuator 180 are also shown. Each furnace comprises a shielding metal canister and an insulated crucible. In one embodiment, a stainless steel tray comprises a hollow chain link box that protects the electrical cables that feed into furnace (e.g., conducting about 20 Amps) from bending, snapping, or being damaged during operation.

[0065] FIG.1J shows interface 120 and interfaces 121 to which an optional mass balance 122 (e.g., a quartz crystal microbalance) or other electrical connections may be connected. Mass balance 122 may be used to monitor the evaporation / sublimation rate of the oxidant. 12 29290897.1PATENT Attorney Docket No.: 3122025 WO01

[0066] In one embodiment, four furnaces move out of synch with each other such that the coating is substantially uniform, without shadowing from the cones vapor rising from each furnace. Advantageously, using two furnaces per unit in line with one another increases the thickness of coating. Additionally, the process may continue even when one furnace or even both furnaces in one unit fail without needing to shut down system.

[0067] FIGS.2A through 2D illustrate the movement of furnaces 170 from oxidant filling system 190 (FIG.1A) to the edge of substrate within chamber 110 (FIG.2B). Actuator 180 continues to move furnace 170 across chamber 110 until it reaches the other edge of substrate (FIG.2D). The actuator then reverses direction and furnace 170 travels back toward the opposite edge of substrate 101. Actuator 180 is also configured to return furnace 170 to oxidant filling system 190 to be filled with oxidant. Suitable actuators include moving ball screws, rotary rack and pinion, servomechanisms, hydraulic pistons, relays, comb drives and electric motors. In one embodiment, actuator 180 is a rotary rack and pinion.

[0068] In one aspect, the actuator(s) 180 are further configured to deliver power to the corresponding furnace(s) 170 from the power supply. In exemplary embodiments, the actuator(s) 180 comprise ball screw actuator(s). Advantageously, moving each furnace in this manner enables coating of wider substrates without the use of multiple stationary furnaces, which are expensive, heavy, and cannot easily be refilled without stopping the process. The disclosed systems and methods also increase the uniformity of coatings and reduce shadowing effects resulting from different oxidant density at different radiuses from the center of the cone.

[0069] Therefore, in one embodiment, the chamber further comprises monomer delivery system 140. In exemplary embodiments, the monomer inlet comprises a plurality of openings proximal to the substrate and configured to release monomer vapor. In the embodiment shown in FIGS.4A–4E, stainless steel tubing delivers monomer, e.g., EDOT vapor, from a source tube and flexible corrugated stainless steel pipe that connect to a monomer supply outside of the chamber. Heaters on the outside of the chamber and resistive tape heaters on interior pipes inlets can be included to facilitate evaporation of the EDOT. Additional inert gases, such as nitrogen or argon, can be introduced into the chamber from a second gas inlet to control the process pressure and to deliver EDOT vapors. Vapor phase oligomerization and polymerization of EDOT is expected to occur in the regions where the monomer vapor flux 13 29290897.1PATENT Attorney Docket No.: 3122025 WO01 intersects with the conical FeCl3vapor plume, and the resulting oligomers, which possess comparatively low kinetic energy, coats any surface placed within this region. Actuator 123 and a series of connectors may be used to raise and lower rollers, and thus the substrate, and monomer delivery system 140 farther and closer to furnaces 170. The connectors position the substrate within 0.001 inch of monomer delivery system 140. FIG 4B. shows a reducer valve that connects a central pipe (e.g., half inch pipe that has no holes) to orthogonal pipes (e.g., quarter inch pipes) that have holes facing upward toward where the substrate would pass. Resistive heating tape is shown on the bottom of each pipe. FIG.4C shows a T-connector that caps the piping grid. Embodiments, such as the one shown in FIGS.4A–4E deliver a substantially uniform monomer vapor concentration to the substrate. Optional KF Flanges allow for electrical connections to be added (FIG.4D). FIG.4E provides a close-up view of the piston arm in one embodiment of actuator 123. A process pressure of 100-1000 mTorr during deposition translates into mean free paths on the order of millimeters for these reactive oligomers. Since these mean free paths are commensurate with the surface roughness of woven fabrics, the oligomers described herein are be able to sample multiple sites before finally adhering to a particular surface, yielding conformal coatings.

[0070] The total deposition rate and film thickness values during vapor deposition depends on the substrate speed and other factors, including monomer concentration, oxidant concentration, and temperature. In one embodiment, the EDOT and FeCl3 flow rates are matched during deposition. Unreacted EDOT or FeCl3remain trapped in the films if their flow rates are mismatched, which are leached out of the film during rinsing. Taking this into account, typical polymer growth rates are about 10 – 15 nanometers per minute of exposure to the reactive vapor cone.

[0071] Further details regarding electrically conductive fabrics and yarns may be found in, PCT Publication No. WO2021194931A1 (Andrew, Baima and Beach), published September 30, 2021, and entitled “Print Heads and Continuous Processes for Producing Electrically Conductive Materials;” U.S. Patent Publication No. 2019 / 0230745A1 (Andrew, Zhang and Baima), published July 25, 2019, and entitled “Electrically-Heated Fiber, Fabric, or Textile for Heated Apparel;” and U.S. Patent Publication No. 2018 / 0269006A1 (Andrew and Zhang), published September 20, 2018, and entitled “Polymeric Capacitors for Energy Storage 14 29290897.1PATENT Attorney Docket No.: 3122025 WO01 Devices, Method of Manufacture Thereof and Articles Comprising the Same,” each of which is incorporated herein in its entirety.

[0072] Because the supply of oxidant in the crucible of each furnace will be depleted during continuous operation, in certain aspects, a first dispenser comprises a first reservoir coupled to a first conduit and a first fluidizing valve, wherein the first fluidizing valve is configured to control a first flow of a particulate solid from the first reservoir through the first conduit to a first outlet disposed within the chamber. In some embodiments, the first actuator is further configured move the first furnace to a fifth position, wherein a first crucible of the first furnace is positioned to receive the particulate solid from the first outlet of the first dispenser. In some embodiments, the first dispenser further comprises a first valve between the first reservoir and the first fluidizing valve. In further embodiments, the first dispenser further comprises a second valve between the first valve and the first fluidizing valve.

[0073] In one embodiment, a second dispenser comprises a second reservoir coupled to a second conduit and a second fluidizing valve, wherein the second fluidizing valve is configured to control a second flow of the particulate solid from the second reservoir through the second conduit to a second outlet disposed within the chamber. In some embodiments, the second actuator is further configured move the second furnace to a sixth position, wherein a second crucible of the second furnace is positioned to receive the particulate solid from the second outlet of the second dispenser. In some embodiments, the second dispenser further comprises a third valve between the second reservoir and the second fluidizing valve. In other embodiments, the second dispenser further comprises a fourth valve between the second valve and the second fluidizing valve. In further embodiments, the volume of the reservoir is the same as the volume of the furnace crucible.

[0074] FIG.1G illustrates dispensers 190. Reservoirs 194 receive oxidant, e.g., from hopper 191 (e.g., stainless steel box having a hinged lid and KF clamp to keep out moisture). After oxidant is added to hopper 191, the headspace may be purged with nitrogen or another inert gas to remove moisture or any other gasses that may react with the oxidant. Nitrogen is supplied via a manifold and hoses. Each hopper may also include a powder fluidization pad (e.g., TransFlow® Powder Fluidization Pads) to move oxidant from hopper 191 into reservoir 194. In some embodiments, reservoir 194 have a volume configured dose / aliquot the amount of 15 29290897.1PATENT Attorney Docket No.: 3122025 WO01 oxidant to fill the crucible, e.g., reservoir 194 may have the same or slightly less volume than the corresponding crucible. In one embodiment, the volume of reservoir 194 is about 330 cm3. Valves 192 (e.g., knife valves) are positioned between hopper 191 and reservoirs 194. Fluidizing valves 193 are positioned between valves 192 and 195. In one embodiment, fluidizing valve 193 are air driven (controls shown in green) and force open a perforated plate down from a horizontal into a vertical position, fluidizing the aliquot of oxidant. Valves 196 (e.g., knife valves) control flow of solid / powdered oxidant through a tapered opening to crucibles of furnaces 170. Optionally, after the crucible is full, a metal rod may be used to compress the solid / powdered oxidant to obtain a shot having a hole that facilitates vaporization. Yet another advantage of providing multiple furnaces and dispensers is that filling and vaporization cycles can be staggered. For example, in the system depicted in FIGS.1G and 1H, two to four of furnaces 170 may be deployed, when one of the crucibles is low / empty, one of the waiting furnaces can be deployed, and the empty crucible refilled without stopping the process.

[0075] FIG.1H provides a cross-sectional view of oxidant filling systems 190, hoppers 191, valves 192 and 195, fluidizing valve 193, reservoir 194, furnaces 170, and actuators 180.

[0076] Also shown in FIG.1G are motors 130 for fluidizing valves 193. Gas flow meters may be used to monitor the solid flow rate, which is directly proportional to gas flow rate.

[0077] FIG.1I provides a perspective view of an assembly comprising interface 120, furnaces 170, and actuators 180. In one embodiment, this assembly further comprises a sliding mechanism that enables the assembly to slide out of coating chamber 110 as shown in FIG.1K and IL.

[0078] FIG.3 shows a scale drawing of one embodiment of system 100.

[0079] It should be appreciated, that the disclosure further relates to methods of coating a substrate comprising: feeding the substrate into a chamber, exposing the substrate to a monomer, and vaporizing an oxidant in a first furnace and moving the first furnace from a first position to a second position by a first actuator disposed within the chamber.

[0080] In one embodiment, feeding the substrate into the chamber comprises unrolling the substrate from a spool. In one embodiment, the method further comprises discharging the substrate through an outlet in the chamber. 16 29290897.1PATENT Attorney Docket No.: 3122025 WO01

[0081] In one embodiment, the method further comprises reducing a pressure in the chamber to about 0.1–1,000 millitorr, about 1–900 millitorr, about 100–800 millitorr, about 200–700 millitorr, about 250–600 millitorr, or about 300–500 millitorr.

[0082] In one embodiment, exposing the substrate to a monomer comprises flowing monomer through a plurality of openings proximal to the first actuator between the first and second positions and configured to release monomer vapor. In one embodiment, wherein the monomer comprises 3,4-ethylenedioxythiophene.

[0083] In one embodiment, the first actuator delivers power from the power supply to the first furnace.

[0084] In one embodiment, the method further comprises vaporizing an oxidant in a second furnace and moving the second furnace from a third position to a fourth position by a second actuator disposed within the chamber.

[0085] In one embodiment, the first actuator moves the first furnace by to a fifth position, such that a first crucible of the first furnace is positioned to receive the oxidant from a first dispenser having a first outlet disposed within the chamber.

[0086] In one embodiment, the method further comprises dispensing the oxidant from the first reservoir to the first crucible of the first furnace disposed within the chamber. In some embodiments, dispensing the oxidant comprises flowing, by a first fluidizing valve, at least a portion of the oxidant from the reservoir to the crucible. In one embodiment, the method further comprises closing a first valve between the first reservoir and the first fluidizing valve. In one embodiment, the method further comprises replacing or refilling the first reservoir with oxidant.

[0087] In one embodiment, the second actuator movies the second furnace to a sixth position, such that a second crucible of the second furnace is positioned to receive the oxidant from a second dispenser having a second outlet disposed within the chamber. In some embodiments, the method further comprises dispensing the oxidant from the second reservoir to a second crucible of the second furnace disposed within the chamber. In some embodiments dispensing the oxidant comprises flowing, by a second fluidizing valve, at least a portion of the oxidant from the reservoir to the crucible. 17 29290897.1PATENT Attorney Docket No.: 3122025 WO01

[0088] In one embodiment, the method further comprises closing a second valve between the second reservoir and the second fluidizing valve. In one embodiment, the method further comprises replacing or refilling the second reservoir with oxidant.

[0089] In one embodiment, the oxidant comprises an iron salt, e.g., FeCl3.

[0090] Optionally, the coated substrate is moved to a cleaning chamber. A post-deposition rinse in the cleaning chamber removes residual FeCl3 trapped in the vapor deposited polymer films and yields metal free, PEDOT-Cl coated substrates. The post deposition rinse contains a dilute aqueous solution, 0.001 – 0.1 moles per liter, of an acid, either monoprotic or diprotic, and it will further dope the PEDOT film to improve the conductivity of the resulting coated substrate. After rinsing, warm air may be blown through the substrate accelerate drying.

[0091] The disclosure also envisions systems, processes, and methods further comprise coating the substrate in a liquid repellant material before and / or after the substrate is coated with electrically conductive polymer. Therefore, in one embodiment, a system comprises a process chamber for coating a flexible substrate, resulting in a liquid repellant substance. In some embodiments, liquid repellant coatings are applied on the substrate under and / or over an electrically conductive substance to produce an electrically conductive material, such as an electrically conductive textile. Depending on the embodiment, the system comprises a second process chamber for encapsulating the electrically conductive material with an encapsulating substance. Both continuous and non-continuous coatings are contemplated. Additionally, coatings may penetrate into the substrate, or not, depending on the properties of the coating substance and substrate, e.g., porosity and wettability.

[0092] In some embodiments, methods and processes further comprise preparing liquid repellant coatings, e.g., acrylate or polysiloxane coatings, that are applied to substrates via vapor deposition and condensation of siloxane monomers, dimers, trimers, or other oligomers as described in WO2022232583 (Andrew, Beach, and Nandy), published November 2, 2022, and entitled “Producing Coated Textiles Using Photo-Initiated Chemical Vapor Deposition;” and PCT / US2022 / 049648 (Andrew, Kelliher, Cali, Monroe, Beach, and Nandy), filed November 11, 2022, and entitled “System, Method and Composition for Producing Liquid Repellant Materials.” 18 29290897.1PATENT Attorney Docket No.: 3122025 WO01

[0093] For example, the coated, optionally cleaned, substrate is moved to an encapsulating chamber. To encapsulate the PEDOT-Cl coated substrate with a coating, a second vapor deposition chamber may comprise a design adapted from previous efforts on the in situ radical chain polymerization of acrylate monomers. In some embodiments, liquid repellant coatings are produced by polymerization of siloxane monomers. Exemplary components of this chamber comprise: a shallow, cylindrical stainless steel shell with small ports for gas flow in and out, heated filaments (typically nichrome) that can be resistively heated to 150-400°C, and an optional liquid-cooled stage on which the substrate is placed / cooling zone. For polymer film growth, an initiator and a monomer are vaporized by heat and reduced pressure. The vapors are then flowed over heated filaments to decompose the initiator into reactive radicals. The radical species and monomer condense on any substrate on the cooled stage, and the polymerization reaction occurs. Films are typically grown at pressures between 0.1-500 mTorr, and the rate of growth can be adjusted by changing the partial pressures of the initiator and monomer, chamber pressure and filament temperature. Typical polymer growth rates are 10 nm per minute of exposure to the reactive vapor. This encapsulation process is comparatively simpler and faster than the previous PEDOT-Cl coating operation and does not require a post- deposition rinse. In another embodiment, this process can also be achieved using UV light (wavelength <400 nm) in place of the wire heating filament to initiate the polymerization. For the light-initiated version, 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, the heated filament array is not needed, and a photoinitiator is used in place of a thermally-activated initiator.

[0094] With respect to both the coating and encapsulation steps, the coating thickness can be varied from approximately 100 to 1000 nm. Highly-uniform and conformal coatings have been formed on an array of substrate surfaces that are exposed to the reactive vapor in both chambers, without any special pre-treatment or fixing steps. Although pre-treatment (e.g., plasma treatment) and / or fixing steps are also contemplated. Further, polymer films are uniformly deposited (macroscopically) over the surface while also conformally wrapping (microscopically) the curved surface of each exposed fibril of the threads constituting the substrate. The high conformality of the conductive coating is expected to be particularly apparent in the SEM images of PEDOT-Cl coated textiles, where the PEDOT-Cl film may 19 29290897.1PATENT Attorney Docket No.: 3122025 WO01 contour to all the exposed surface features of the substrate with high fidelity over multiple length scales. Cross-section SEM studies are expected to confirm that the PEDOT and protective acrylate films are purely surface coatings and that the bulk of fibrils / threads are not swelled or dyed by the polymers. Successful vapor coatings may be carried out without any pre-treatment steps, regardless of surface chemistry, thread / yarn composition and weave density. The polymer coatings are expected not to change the feel of any of the substrates, as determined by touching the substrates with bare hands before and after coating. Further, the coatings are expected not increase the weight of the substrates by more than 2%.

[0095] In order to increase the coating thickness and throughput, the total dwell time in a deposition zone and the stage temperature may be adjusted. The local temperatures and corresponding regions of yarn can be used to correlate the effect of temperature with better resolution. Chamber pressures can also be used to tightly-control coating uniformity while increased throughput speed. Increased (>300 mTorr) chamber pressures then result in shorter mean free paths for the chemical species responsible for polymer chain growth in the chamber, which, in turn, afford greater surface coverage due to a higher frequency of surface-restricted reactions and suppression of line-of-sight deposition events.

[0096] The substrate upon which the film is disposed is an electrically insulating substrate. Electrically conducting substrates are those that have an electrical volume resistivity of less than or equal to 1×1011ohm-cm, while electrically conducting substrates are those that have an electrical volume resistivity of greater than 1×1011ohm-cm. The substrate may be in the form of a slab, a thin film or sheet having a thickness of several nanometers to several micrometers (e.g., 10 nanometers to 1000 micrometers), woven or non-woven fibers, yarns, a fabric, a gel, a pixel, a particle, or the like. The substrate may have a smooth surface (e.g., not deliberately textured) or may be textured.

[0097] The substrate may have a surface area of a few square millimeters to several thousands of square meters. In an 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.

[0098] In an embodiment, electrically insulating substrates may include ceramic substrates, or polymeric substrates. Ceramic substrates include metal oxides, metal carbides, metal nitrides, 20 29290897.1PATENT Attorney Docket No.: 3122025 WO01 metal borides, metal silicides, metal oxycarbides, metal oxynitrides, metal boronitrides, metal carbonitrides, metal borocarbides, or the like, or a combination thereof. Examples of ceramics that may be used as the substrate 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 boride compounds (SiBn, where n=14, 15, 40, and so on) (e.g., silicon triboride, SiB3, silicon tetraboride, SiB4, silicon hexaboride, SiB6, or the like), or the like, or a combination thereof.

[0099] In some embodiments, ceramics, alone or in combination with other materials, can be deposited on a substrate. Exemplary ceramics include, but are not limited to, barium titanate, barium titanate mixed with strontium titanate, bismuth strontium calcium copper oxide, a high- temperature superconductor, boron nitride, ferrite, lead zirconate titanate (PZT), magnesium diboride (MgB2), porcelain, silicon containing inorganic, such as sialon (Silicon Aluminium Oxynitride), silicon carbide (SiC), silicon nitride (Si3N4), steatite (magnesium silicates), titanium carbide, uranium oxide (UO2), Yttrium barium copper oxide (YBa2Cu3O7-x), zinc oxide (ZnO), and zirconium dioxide (zirconia).

[0100] Organic polymers that are electrically insulating may also be used as the substrate and may be selected from a wide variety of thermoplastic polymers, blend of thermoplastic polymers, thermosetting polymers, or blends of thermoplastic polymers with thermosetting polymers. The organic polymer may also be a blend of polymers, copolymers, terpolymers, or combinations comprising at least one of the foregoing organic polymers. The organic polymer can also be an oligomer, a homopolymer, a copolymer, a block copolymer, an alternating block copolymer, a random polymer, a random copolymer, a random block copolymer, a graft copolymer, a star block copolymer, a dendrimer, a polyelectrolyte (polymers that have some repeat groups that contain electrolytes), a polyampholyte (a polyelectrolyte having both cationic and anionic repeat groups), an ionomer, or the like, or a combination comprising at last one of the foregoing organic polymers. The organic polymers have number average molecular weights greater than 10,000 grams per mole, preferably greater than 20,000 g / mole and more preferably greater than 50,000 g / mole.

[0101] Examples of the organic polymers are polyacetals, polyolefins, polyacrylics, polycarbonates, polystyrenes, polyesters, polyamides, polyamideimides, polyarylates, 21 29290897.1PATENT Attorney Docket No.: 3122025 WO01 polyarylsulfones, polyethersulfones, polyphenylene sulfides, polyvinyl chlorides, polysulfones, polyimides, polyetherimides, polytetrafluoroethylenes, polyetherketones, polyether etherketones, polyether ketone ketones, polybenzoxazoles, polyphthalides, polyanhydrides, polyvinyl ethers, polyvinyl thioethers, polyvinyl alcohols, polyvinyl ketones, polyvinyl halides, polyvinyl nitriles, polyvinyl esters, polysulfonates, polysulfides, polythioesters, polysulfones, polysulfonamides, polyureas, polyphosphazenes, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polytetrafluoroethylene, perfluoroelastomers, fluorinated ethylene propylene, perfluoroalkoxyethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polysiloxanes, or the like, or a combination thereof.

[0102] Examples of polyelectrolytes are polystyrene sulfonic acid, polyacrylic acid, pectin, carrageenan, alginates, carboxymethylcellulose, polyvinylpyrrolidone, or the like, or a combination thereof.

[0103] 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, or the like, or a combination thereof.

[0104] The polymers and / or ceramics may be in the form of films, fibers, single strands of fiber, woven and non-woven fibers, woven fabrics, slabs, or the like, or a combination thereof. The fibers may be treated with surface modification agents (e.g., silane coupling agents) to improve adhesion if desired.

[0105] In addition to fibers, fabrics, yarns and textiles, the present technique may be used to coat and / or encapsulate other substrates of interest for other applications. For instance, exemplary substrates are flat sheets, such as paper, foil, Tyvek, polymeric sheets including the polymer sheets listed above, porous, planar membranes, such as CELGARD®, or cylindrical or curved objects, such as monofilament NYLON® thread, single-ply silk thread, or monofilament fiberglass thread. 22 29290897.1PATENT Attorney Docket No.: 3122025 WO01

[0106] Suitable substrates further comprise plastics, metallized plastics, and metal foils. Exemplary substrates comprise greater than 80%, 70%, 60%, 50%, or 40% by atomic composition of metals. The contemplated thickness of the metal layers of exemplary metallized plastics (e.g., metallized plastics used in chip bags) comprise less than 100 nm coating of metals on a plastic substrate.

[0107] Optionally, substrates are pre-treated, e.g., by exposure to an inert gas plasma, to activate the surface and increase bonding between the substrate and the deposited material. In some embodiments, pretreatment steps comprise roughening, polishing, silane deposition, electron beam, IR radiation, gamma radiation, plasma exposure, thermal treatment, and / or laser exposure.

[0108] In regard to liquid repellant substances, in one embodiment, the liquid repellent substance comprises polysiloxane. In one embodiment, liquid repellant substance is deposited on a substrate to which an electrically conductive polymer has already been deposited. In another embodiment, liquid repellant substance is deposited on a substrate to which no electrically conductive polymer has been applied. In a further embodiment, an electrically conductive polymer is deposited on the liquid repellant substance as described above. Optionally, a substrate to which liquid repellant polymer and electrically conductive polymer have been applied is coated with another layer of liquid repellant substance, e.g., sandwiching the electrically conductive polymer between layers of liquid repellant material. It should be appreciated that the coatings and layers disclosed herein need not be continuous and may or may not penetrate into the substrate and any previously applied coating materials.

[0109] Examples of polysiloxanes include those resulting from the condensation of an alkylhalosiloxane, e.g., chlorosilane, dichlorosilane and / or trichlorosilane monomer with a diol and / or water as shown in Scheme 1. In some embodiments, the silane monomer and diol are vaporized and mixed at the time of coating. Exemplary chlorosilanes comprise one, two, or three alkyl groups bonded to each silicon atom. In further examples, halosilanes, such as bromo-, iodo-, and fluorosilanes are used as monomers. Exemplary alkyl groups (“R”) include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl or greater. It should be appreciated that alkyl groups may be branched or unbranched. Exemplary silanes comprise two alkyl groups that are the same (e.g., dimethyldichlorosilane, diethyldichlorosilane, 23 29290897.1PATENT Attorney Docket No.: 3122025 WO01 diisopropyldichlorosilane), and in another embodiment, the silane includes two alkyl groups that are different (e.g., n-propylmethyldichlorosilane), As shown in Scheme 1, monomers may comprise dihalosilane (e.g., dichlorosilane) dimers, trimers, tetramers, pentamers, hexamers, heptamers, octomers and / or other oligomers.

[0110] Exemplary diols include alkyl diols having one to eight carbon atoms, which may be linear or branched (e.g., dihydroxymethane, ethyleneglycol, propylene glycol, etc.) as shown in Scheme 1. Examples of diols also comprise polyethylene glycols having between one and eight ethylene units. Use of polypropylene glycols is also contemplated. Scheme 1

[0111] In some examples, a ratio of silane monomer to water and / or diol 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 by volume.

[0112] Silane monomers react with water and / or a diol in one of the chambers disclosed herein (e.g., 110, 130, 210, 230, 410, 630A, 630B, 300A, 300B). In some embodiments, the formulation includes a disiloxane or trisiloxane monomer that is vaporized at the time of coating, and mixed at the time of coating with vapors of an aryl or diarylketone photoinitiator, 24 29290897.1PATENT Attorney Docket No.: 3122025 WO01 and ultraviolet light of any wavelength lower than 400 nm. In other embodiments, the formulation includes a disiloxane or trisiloxane monomer that is vaporized at the time of coating and mixed at the time of coating with vapors of a diol, glycol and / or water in the presence of an electrically generated reactive ion plasma, such as an argon ion plasma. In all embodiments, a vacuum chamber with a plurality of ports needs to be used to mix and therefore induce a reaction between vapors of the silane or siloxane monomer and the co-reactant to form a polymer coating directly on the surface of any desired substrate. Substrates can comprise, paper, yarns, fibers and textiles that are woven, knit 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, as defined as the total duration of time wherein the vapors of the monomers and various co-reactants are allowed to mix within the process chamber controls the thickness of the polysiloxane coating that is 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.

[0113] Polysiloxane coating thicknesses of less than one hundred micrometers result in liquid repellent textiles and yarns. The relative ratio of the siloxane monomer and co-reactant vapors can be controlled to increase or decrease the degree of polycondensation between polymer chains i.e., the crosslink density, and to increase or decrease the average polymer molecular weight of the polysiloxane coating. The crosslink density and polymer molecular weight can also be increased by introducing optional ultraviolet light or an electrically-generated reactive ion plasma into the process chamber at the same time as the monomer and co-reactant vapors are introduced into the chamber.

[0114] In further regard to liquid repellant substances, in one embodiment, the liquid repellent substance comprises poly(acrylate). In one embodiment, a method of coating a substrate with a liquid repellent polymer comprises vaporizing an acrylate, vaporizing a diacrylate, 25 29290897.1PATENT Attorney Docket No.: 3122025 WO01 vaporizing an initiator, and initiating the polymerization of the acrylate and the diacrylate on a substrate.

[0115] Exemplary acrylates comprise 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 comprises 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate.

[0116] Exemplary diacrylates comprise alkyldiol diacrylates, such as 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate and 1,6-hexanediol diacrylate. In one embodiment, the diacrylate comprises 1,4-butanedioldiacrylate.

[0117] Polymerization may be initiated by heat and / or light. In one embodiment, the initiator comprises a photoinitiator, e.g., 2-hydroxy-2-methylpropiophenone.

[0118] Contemplated systems for producing protected and / or electrically conductive material in which the material is continuously fed during processing comprise an oxidative chemical vapor deposition system, a cleaning system, and an initiated chemical vapor deposition chamber, each designed to maintain the appropriate vacuum notwithstanding the entrance of the substrate and exit of the coated / protected material. In one embodiment, the substrate is first fed through a coating chamber. Next, the substrate is continuously fed to a cleaning chamber. Next, the substrate is continuously fed to an encapsulating chamber.

[0119] In one example, the vacuum can be maintained using self-induced friction amplification, in which pulling the substrate in a given direction causes the opening to clamp tighter on the substrate to create a seal. A well-known example of this type of sealing is the popular finger trap toy or towing stock device. In another example, an external vacuum housing similar to a glove box could also be implemented to maintain vacuum while feeding substrate into the deposition chamber(s).

[0120] In yet another example, a single chamber could be used that includes all of the functions of the three chambers e.g., in large scale factory production. EXAMPLES

[0121] Many examples of the utility of the present disclosure have been contemplated by the inventors, including heated gloves, hats, and other clothing, printed circuits that are embedded 26 29290897.1PATENT Attorney Docket No.: 3122025 WO01 onto clothing to form wearable devices, etc. Various other applications of the present disclosure have been contemplated, including wearables that provide heat to a user, monitor the users health by measuring electric signals and temperatures, allow for mounting of other components such as blood pressure or oxygen sensors, etc.

[0122] Therefore, and as discussed above, generally stated, provided herein are a variety of techniques for coating electrically conductive polymer onto substrates including flat or smooth plastic, paper, transparent conducting oxide or metal oxide surface, or nonwoven, prewoven or knit fabric surface that is encapsulated with an insulating material. The various components FIGS. 1-6B can be rearranged or combined in different ways to construct systems for producing the material. For instance, any of the chambers 110, 120, 130, 210, 220, 230, 410, 520, 630A, or 630B can be mixed and matched to provide a system in accordance with 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 have only been touched upon, such as the use of an inert carrier gas to carry the chemicals through the process chamber, the use of vacuum pumps to maintain a vacuum, the use of motors and other details of the spooling mechanism, etc., that a person of ordinary skill in the art would understand.

[0123] The fact that one or more specific embodiments for coating, cleaning and encapsulating have been used to illustrate the concepts of the present technique are not meant to limit the disclosure in any manner. Indeed, as noted above, the concepts disclosed herein are not limited to the disclosed substrates (e.g., textiles, yarns, fibers or fabrics). For example, many other applications of the different processes described herein have been envisaged by the inventors and are included within the scope of this disclosure. The presentation of a specific set of claims herein is not meant to limit scope, but is only done to illustrate some of the example embodiments which are covered by this disclosure. For example, the techniques described herein may be scaled in size from a large factory embodiment measuring many yards in each direction down to a smaller table-top apparatuses that are only a few feet in size. In addition to fiber, fabric, and yarn embodiments, the present disclosure could be used for producing circuits that are printed on any of the substrates identified above, and the coating and encapsulation process can be used to form the conductive lines of the circuit. By adding other electrical or 27 29290897.1PATENT Attorney Docket No.: 3122025 WO01 semiconductor elements in a manner known in the art, the end product would be a wearable or non-wearable circuit or electronic device that could be conformed to any surface or configuration, providing great advantages compared to flat circuit boards presently used in the field. 28 29290897.1

Claims

PATENT Attorney Docket No.: 3122025 WO01 Claims:

1. A system for coating a substrate comprising: a chamber; a first actuator disposed within the chamber and configured to move a first furnace from a first position to a second position; and a power supply configured to deliver power to the first furnace.

2. The system of claim 1, wherein the chamber comprises an inlet configured to continuously receive the substrate from a spool.

3. The system as in either claim 1 or claim 2, wherein the chamber comprises an outlet configured to continuously discharge the substrate.

4. The system of any preceding claim, wherein the chamber is configured to maintain a pressure of about 0.1–1,000 millitorr, about 1–900 millitorr, about 100–800 millitorr, about 200–700 millitorr, about 250–600 millitorr, or about 300–500 millitorr.

5. The system of any preceding claim, wherein the chamber further comprises a monomer inlet.

6. The system of claim 5, wherein the monomer inlet comprises a plurality of openings proximal to the first actuator between the first and second positions and configured to release monomer vapor.

7. The system as in any preceding claim, wherein the first actuator is further configured to deliver power to the first furnace from the power supply.

8. The system as in any preceding claim, wherein the first actuator comprises a rotary rack and pinion actuator.

9. The system as in any preceding claim further comprising a second actuator disposed within the chamber and configured to move a second furnace from a third position to a fourth position.

10. The system as in any preceding claim, further comprising a first dispenser, wherein the first dispenser comprises a first reservoir coupled to a first conduit and a first fluidizing valve, wherein the first fluidizing valve is configured to control a first flow of a 29 29290897.1PATENT Attorney Docket No.: 3122025 WO01 particulate solid from the first reservoir through the first conduit to a first outlet disposed within the chamber.

11. The system of claim 10, wherein the first actuator is further configured move the first furnace to a fifth position, wherein a first crucible of the first furnace is positioned to receive the particulate solid from the first outlet of the first dispenser.

12. The system as in either claim 10 or claim 11, wherein the first dispenser further comprises a first valve between the first reservoir and the first fluidizing valve.

13. The system of claim 12, wherein the first dispenser further comprises a second valve between the first valve and the first fluidizing valve.

14. The system as in any one of claims 10-13, further comprising a second dispenser, wherein the second dispenser comprises a second reservoir coupled to a second conduit and a second fluidizing valve, wherein the second fluidizing valve is configured to control a second flow of the particulate solid from the second reservoir through the second conduit to a second outlet disposed within the chamber.

15. The system of claim 14, wherein the second actuator is further configured move the second furnace to a sixth position, wherein a second crucible of the second furnace is positioned to receive the particulate solid from the second outlet of the second dispenser.

16. The system as in either claim 14 or claim 15, wherein the second dispenser further comprises a third valve between the second reservoir and the second fluidizing valve.

17. The system of claim 16, wherein the second dispenser further comprises a fourth valve between the second valve and the second fluidizing valve.

18. The system as in any one of claims 10-17, wherein the a volume of the first reservoir is the same as the volume of the first crucible, and the volume of the second reservoir is the same as the volume of the second crucible.

19. A method of coating a substrate comprising: feeding the substrate into a chamber; exposing the substrate to a monomer; and vaporizing an oxidant in a first furnace and moving the first furnace from a first position to a second position by a first actuator disposed within the chamber. 30 29290897.1PATENT Attorney Docket No.: 3122025 WO01 20. The method of claim 19, wherein feeding the substrate into the chamber comprises unrolling the substrate from a spool.

21. The method as in either claim 19 or claim 20 further comprising discharging the substrate through an outlet in the chamber.

22. The method of any one of claims 19-21 further comprising reducing a pressure in the chamber to about 0.1–1,000 millitorr, about 1–900 millitorr, about 100–800 millitorr, about 200–700 millitorr, about 250–600 millitorr, or about 300–500 millitorr.

23. The method of any one of claims 19-22, wherein exposing the substrate to a monomer comprises flowing monomer through a plurality of openings proximal to the first actuator between the first and second positions and configured to release monomer vapor.

24. The method as of any one of claims 19-23 further comprising deliver power to the first furnace from the power supply by the first actuator.

25. The method of any one of claims 19-24 further comprising vaporizing an oxidant in a second furnace and moving the second furnace from a third position to a fourth position by a second actuator disposed within the chamber.

26. The method of any one of claims 19-25 further comprising moving the first furnace by the first actuator to a fifth position, wherein a first crucible of the first furnace is positioned to receive the oxidant from a first dispenser having a first outlet disposed within the chamber.

27. The method of claim 26 further comprising dispensing the oxidant from the first reservoir to the first crucible of the first furnace disposed within the chamber.

28. The method of claim 27, wherein dispensing the oxidant comprises flowing, by a first fluidizing valve.

29. The method as in either claim 27 or claim 28 further comprising closing a first valve between the first reservoir and the first fluidizing valve.

30. The method of claim 29 further comprising replacing or refilling the first reservoir with oxidant.

31. The method as in any one of claims 26-30 further comprising moving the second furnace by the second actuator to a sixth position, wherein a second crucible of the second 31 29290897.1PATENT Attorney Docket No.: 3122025 WO01 furnace is positioned to receive the oxidant from a second dispenser having a second outlet disposed within the chamber.

32. The method of claim 31 further comprising dispensing the oxidant from the second reservoir to a second crucible of the second furnace disposed within the chamber.

33. The method of claim 32, wherein dispensing the oxidant comprises flowing, by a second fluidizing valve.

34. The method as in either claim 32 or claim 33 further comprising closing a second valve between the second reservoir and the second fluidizing valve.

35. The method of claim 34 further comprising replacing or refilling the second reservoir with oxidant.

36. The method as in either claim 28 or claim 33, wherein the a volume of the first reservoir is the same as the volume of the first crucible, and the volume of the second reservoir is the same as the volume of the second crucible.

37. The method as in any one of claims 26-36, wherein the monomer comprises 3,4- ethylenedioxythiophene.

38. The method as in any one of claims 26-37, wherein the oxidant comprises FeCl3.

39. The method as in any one of claims 26-38 further comprising coating the substrate in a liquid repellant material. 32 29290897.1

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