Plasma coloring and pigment fixing method and system

Abstract

A system for coating an article includes a pigment applicator adapted to apply a pigment and a plasma module adapted to generate a plasma region. At least one of a chemical and a precursor is supplied to the plasma generated in the plasma region, such that the plasma region is capable of at least partially polymerizing at least one of the chemical and the precursor to form a plasma-polymerized coating. The pigment can be fixed to the article by the plasma-polymerized coating.

Description

[Technical Field]

[0001] This disclosure relates to applying color to a substrate for the purpose of changing the visual appearance of the substrate. More particularly, this disclosure is directed to the application of dyes or pigments fixed to the substrate by a plasma process. [Background technology]

[0002] Conventional dyeing methods are well known in the field of textile manufacturing, however, these conventional methods are generally wasteful and unsustainable for future dyeing of textiles and dyeing or coloring of other articles.

[0003] Often, these processes require significant amounts of water, chemicals, and / or fossil fuels to produce a finished product. Furthermore, the dyeing stage of textile preparation may be one of many steps that requires passing the textile through a stenter or other system to dry it. Furthermore, depending on the textile dyeing or coloring process, specific processes are likely required for natural or synthetic fibers or different textile compositions, thereby increasing the complexity of these processes for different materials.

[0004] Given the significant challenges faced by conventional dyeing systems and methods, there may be a need to replace existing methods and systems with more efficient and / or environmentally friendly alternatives to alleviate one or more problems.

[0005] Typically, textile materials may include materials such as fibers, yarns, cloth, and fabrics made therefrom. The textile colorant in a conventional process may be provided as a liquid, generally a solvent, for dissolving the dye, or a solution or dispersion containing a pigment or powder.

[0006] Textile colorants are used to color textiles, and the colorant is typically the color imparted to the textile, but the textile can enhance or change its color based on the opacity or other properties of the dye or pigment. While the bond between the colorant and the textile is generally desired to be permanent, the bond strength is often less than desirable.

[0007] Some colorants chemically bond to the textile, others are physically trapped within the textile fibers, and others require additional fixatives to bind the colorant to the textile. Dyes and pigments are commonly used to color textiles; dyes are generally provided in solution, while pigments are generally insoluble.

[0008] Dyes are generally used to penetrate fibers and impart color to fibers from within the fiber. In contrast, pigments generally cannot penetrate fibers, but are deposited around the fiber and require a binder or other adhesive to hold the pigment in place. Because these coloring mechanisms are significantly different, the methods for applying them to textiles to color them are also significantly different.

[0009] Dyes are generally water-soluble and may have an affinity to bond with certain textiles. Fabrics and dyes are generally attracted to each other through chemical interactions between the textile fibers and the dye. Some dyes are reactive dyes, attaching to color molecules so that some of the dye reacts with the textile fibers, causing the color molecules to attach to the fibers and remain the desired color. Such chemical reactions can form many different bonds of varying bond strengths.

[0010] Pigments are generally not attracted to the fibers of the fabric and rely on a secondary component or binder to adhere to the fibers. The pigments are dissolved or suspended in a solution based on a carrier medium.

[0011] In either case, the application of a pigment or dye colorant requires at least one wet process used to apply the colorant to the treated textile. Wet process and drying equipment are generally fairly large and expensive pieces of equipment and also introduce many complexities into textile processing. These complexities relate to fabric stiffening, shrinkage, stiffness, drapeability, and hand feel after processing. These complexities may require the addition of additional chemicals to the wet processing step to address these complexities during drying, or simply for the coloring process itself. Furthermore, some of these additional chemicals may result in the visual presence of chalk marks or other defects that may require further processing steps to resolve before the textile is suitable for inclusion in a final product.

[0012] Traditional dyeing processes typically consume significant amounts of water and often result in the release of large amounts of waste chemicals, such as dyes, into the environment. Dyes can significantly detract from the aesthetics of water bodies, increase biochemical and chemical oxygen demand (BOD and COD), inhibit photosynthesis, hinder plant growth, enter the food chain, cause persistence and bioaccumulation, and promote toxicity, mutagenicity, and carcinogenicity. Therefore, reducing wastewater is advantageous.

[0013] Considering the drawbacks and limitations of conventional dyeing methods, it would be desirable to improve, modify, or replace existing methods with more environmentally friendly methods and systems to practice the methods.

[0014] Any discussion of prior art throughout this specification should in no way be taken as an admission that such prior art is widely known or forms part of the common general knowledge in the field. Summary of the Invention

[0015] Problem to be solved It would be advantageous to provide a system and / or method that can be used to dye natural and synthetic materials.

[0016] It would be advantageous to provide a system capable of dyeing or coloring a substrate that reduces water consumption.

[0017] It would be advantageous to provide a system that can reduce carbon emissions compared to traditional dyeing and finishing processes.

[0018] It would be advantageous to provide a system that can provide the dyeing and finishing processes in a single roll-to-roll process.

[0019] It may be advantageous to provide a dyeing method that allows for coloring of one side of a substrate.

[0020] It would be advantageous to provide new dyeing methods that require fewer resources.

[0021] It can be advantageous to provide a dyeing method that is a dry dyeing method.

[0022] It can be advantageous to provide a fixing and / or bonding process that can fix or capture particles, pigments and / or powders to the surface of an article.

[0023] It would be advantageous to provide a method by which substrates can be dyed more efficiently.

[0024] It would be advantageous to provide methods and processes that can attach particles to the surface of an article.

[0025] It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

[0026] Means to solve the problem In a first aspect, a system for coating an article is provided. The system can include a pigment applicator adapted to apply a pigment and a plasma module adapted to generate a plasma region. At least one of a chemical and a precursor can be supplied to the generated plasma region, and the plasma region can at least partially polymerize the at least one of the chemical and the precursor, thereby forming a plasma-polymerized coating, and the pigment can be fixed to the article by the plasma-polymerized coating.

[0027] Preferably, the system further includes a plasma post-treatment module adapted to treat the plasma polymerized coating. Preferably, the pigment applicator is integrated with the plasma module. Preferably, the plasma module is housed in a chamber, and the chamber is locally purged with plasma gas to a purity of greater than 90%. Preferably, the entrance to the chamber is fitted with a roller that seals the entrance, so that the plasma gas is generally contained within the chamber and external fluid intrusion is restricted, while optionally allowing the article to enter the chamber. Preferably, the pigment applied to the article is at least one of a colorant, a functional pigment, and a conductive pigment. Preferably, the plasma module is adapted to supply at least one of a chemical and a precursor to the plasma region, so that the at least one of the chemical and the precursor forms plasma polymerized molecules before being applied to the article to form the plasma polymerized coating.

[0028] In a further aspect, a plasma-coated article is provided. The article can include a surface having a pigment deposited thereon. The pigment is bonded to the article by a plasma-polymerized coating, the plasma-polymerized coating being polymerized at a pressure in the range of 95 kPa to 105 kPa.

[0029] Preferably, a further pigment deposition is applied on the surface of the plasma polymerized coating. Preferably, the further pigment deposition is fixed to the plasma polymerized coating by the further plasma polymerized coating. Preferably, the pigment is provided to the article during the plasma polymerization step, and the pigment is bound within the plasma polymerized coating upon application. Preferably, the pigment is relatively large in size compared to the thickness of the coating. Preferably, the pigment is a colorant of a different color than the color of the article, such that the article is imparted with a hue or a color generally similar to that of the pigment colorant. Preferably, the pigment is a functional pigment adapted to release and / or diffuse ions while bound within the plasma polymerized coating. Preferably, the plasma polymerized coating is finished by a plasma post-treatment step to cure or otherwise treat the exposed surface of the plasma polymerized coating.

[0030] In the present invention, the words "comprise", "comprising" and the like are to be interpreted in an inclusive rather than an exclusive sense, i.e., in the sense of "including, but not limited to".

[0031] The present invention should be interpreted with reference to at least one of the technical problems described in the background art or related technical problems. The present invention aims to solve or ameliorate at least one of the technical problems, which may result in one or more advantageous effects as defined herein and described in detail with reference to preferred embodiments of the present invention. [Brief explanation of the drawings]

[0032] [Figure 1] FIG. 1 is a schematic diagram of a system including one or more processing modules for processing articles. [Figure 2] Figure 2A shows a schematic side view of a system including multiple chambers for processing articles, and Figure 2B shows a side view of a further system for applying colorant to articles. [Figure 3]FIG. 3 shows a side view of another embodiment that can be used to apply colorant to an article. [Figure 4] FIG. 4 shows a side view of one embodiment of a module and distribution system. [Figure 5] Figure 5A shows a side view of one embodiment of a module for generating a plasma region, and Figure 5B shows another side view of Figure 5A showing several different plasma regions or fluid distributions. DETAILED DESCRIPTION OF THE INVENTION

[0033] Preferred embodiments of the invention will now be described with reference to the accompanying drawings and non-limiting examples.

[0034] Described herein is a system for processing and fabricating materials, including substrates, sheets of material, 3D objects, and irregular objects (collectively, "articles" 1). While any desired article 1 can be processed with the system 10, some embodiments may refer to substrates or other planar articles. That is, the system is not limited to use only for processing substrates 1.

[0035] The system 10 shown in various embodiments of the figures includes multiple plasma treatment modules 20 used to treat the substrate 1. These systems are preferably compatible with plasma-enhanced chemical vapor deposition (PECVD) processes, in which plasma can be used to polymerize chemicals, monomers, or precursors to form plasma-polymerized coatings or films. The treatment modules 20 may be showerhead modules, spray modules, deposition modules, plasma modules, or other treatment modules (e.g., treatment modules usable to activate surfaces to receive dry and / or wet coatings that are cured, or to apply coatings to surfaces). If a dispersion is applied, it may be desirable to evaporate or otherwise remove the dispersion before exposure to the treatment module 20. Each module 20 is removably attached to the system 10 and can be used to pre-treat, post-treat, treat, coat, cover, deposit, activate, or perform any desired treatment process on the article 1. Preferably, the treatment applied by the treatment modules 20 includes pigments and / or particulates that are deposited on the article 1 after passing through the plasma from the head, although the pigment applicator 18 may be a separate unit or module capable of applying pigment before being treated by the module 20.

[0036] The article 1 can be transported beneath the processing head 20 by a transport means. Any desired transport means can be used, such as a conveyor, a moving platform, rollers, or other pre-configured means. Figures 1 and 2 show an embodiment of the system 10 that uses rollers to transport the substrate article 1 through the chamber 15.

[0037] In another embodiment, the article 1 can be positioned directly beneath the processing module 20 and processed without being transported from a first location to a second processing location. This is particularly useful when a single article 1 is to be coated or processed, rather than a series of articles on a manufacturing line. In this manner, the system 10 can function as a sterilization device, a surface activation device, or a selective processing system.

[0038] The processing module 20 may enable at least one of physical modification, chemical modification, coating, film application, surface activation, sterilization, polymerization, or other desired processing process. The system 10 may include any number of modules 20 for performing the above processing.

[0039] It will be appreciated that in some embodiments, when using a gas supply or pressurized plasma fluid, chamber 15 may have a pressure above atmospheric pressure. This pressure may be in the range of 10 Pascals to 1 MPa. In some embodiments, the pressure may be in the range of 95 kPa to 110 kPa, with ambient pressure being approximately 101 kPa. In other words, the pressure may be ±5 kPa relative to ambient pressure or 1 atmosphere. Unlike conventional systems, the pressure may increase above atmospheric pressure rather than decreasing toward a vacuum. For this reason, system 10 can be adapted to function at atmospheric pressure or above, which is particularly advantageous. Optionally, the pressure within chamber 15 may have a negative pressure to aid in the extraction of gases and other fluids within chamber 15. The negative pressure in chamber 15 may be in the range of 90 kPa to 100 kPa, or ±10 kPa relative to atmospheric pressure, or in more specific embodiments, ±1 kPa relative to atmospheric pressure.

[0040] Conventional plasma processing equipment typically requires a vacuum or low-pressure chamber in which the article is processed. Because using plasma in a non-vacuum chamber presents numerous challenges, plasma is not typically used outside of a sealed, reduced-pressure chamber. While plasma generation and maintenance are also easier in vacuum systems, the present system 10 can include a generally pure or fluid-controlled chamber at near-atmospheric pressure, addressing this issue. While supplying gas to the chamber 15 may be relatively straightforward, maintaining internal purity while supplying chemicals for polymerization or conducting a polymerization process on chemicals, monomers, or precursors on the article is relatively difficult. Therefore, the system 10 can be configured with a series of interlocks or airlocks that allow the delivery of the article 1 while reducing fluid flow into and / or out of the chamber 15. Additionally, one or more extraction locations and a recycling system 70 can be used to purify and return fluids to the system 10.

[0041] Another issue with vacuum systems is the even or uniform distribution of the carrier fluid and the monomers contained therein. Another issue is the introduction of fluid into the plasma region or reaction gap, which can cause dangerous / undesirable polymerization of molecules or ionization of molecules, which can damage the substrate 1 being treated or affect the quality of the treatment. Therefore, the system module 20 described herein can be used to address these issues.

[0042] In addition to the above, another significant problem with existing systems is the requirement to operate at a vacuum level. Not only does achieving a vacuum take a significant amount of time, but injecting an aerosol typically increases the overall pressure within the vacuum chamber, potentially causing the system to fail. Additionally, aerosols injected into a vacuum tend to dissipate, rendering them unusable. Therefore, the disclosed system and method offer significant advantages over known prior art.

[0043] Another important advantage of the present system 10 is that aerosols can be used to deliver monomers and / or pigments to the plasma region in coating processes. Aerosols can be used to transport pigments, salts, organic particles, or inorganic particles to the plasma region or another desired location within the chamber 15. As described above, atomizers can be used to convert at least one fluid into a vapor or aerosol. The vapor can be considered a form of "mist" that can contain one or more types of monomers and / or one or more types of pigments. Optionally, pigments or other particles can be dispersed within the mist formed by the atomizer or vaporizer.

[0044] The aerosol is delivered to the chamber 15 through the fluid outlet and can then be introduced directly or by gravity into the plasma region. The aerosol is directed toward the plasma region, with at least 50% of the aerosol passing through the plasma region and subsequently deposited on the target area of ​​the article 1. Using this method, coatings of 50 nm / min to 400 nm / min can be achieved. In some embodiments, coatings of 100 nm to 300 nm can be achieved. In yet other embodiments, the coating deposition rate can be about 150 nm / min. The pigment deposition, if applied separately, can be independent of the coating thickness, but can have a deposition rate before the plasma-polymerized coating is formed on the pigment. The pigment loading rate can range from 0.25 g / min per meter width to 360 g / min per meter width, depending on the size of the pigment being applied. In some embodiments, the pigment delivered to the article 1 is about 1.5 g / m 2 ±0.5g / m 2 or generally 0.5 g / m 2 ~5g / m 2The coating thickness may be the thickness of the plasma polymerized coating without the pigment present, or may be in addition to the previously deposited thickness of the pigment. For example, if a 400 nm thick fill or layer of pigment is applied and a 100 nm plasma polymerized coating is applied, the overall coating thickness may be in the range of 400 nm to 500 nm, depending on the overall coverage of the pigment and the ability of the plasma polymerized coating to fill in between the pigments and form a final plasma polymerized coating with the pigment embedded or immobilized therein.

[0045] In contrast, systems utilizing vacuum pressure cannot achieve similar coatings because the introduction of the aerosol into a vacuum or near-vacuum conditions results in high pressure and the aerosol is quickly dispersed throughout the vacuum chamber rather than being delivered to a target area or plasma region 112. Even if the plasma region 112 could be provided at the aerosol exit, plasma irregularities would occur as the aerosol was ejected, causing particles to disperse throughout the chamber and not flow in the desired direction. Other drawbacks are known for conventional systems utilizing vacuum or lower pressures.

[0046] In yet another embodiment, pigments can be incorporated into the aerosol. In this manner, powders or particles of a desired size can be transported through the fluid system into the plasma region 112.

[0047] In another embodiment, a separate stream of pigment or clusters is provided which mixes with the fluid exiting the outlet and is directed towards the plasma region. Optionally, the pigment may be sprayed, knife-applied, wiped or projected onto article 1.

[0048] Referring to FIG. 1 , a system 10 is shown that can be used to process article 1. Article 1 is a substrate that is generally considered planar or 2D in nature and can be processed via a roll-to-roll process. The illustrated article can be a linear substrate, porous, non-porous, woven, nonwoven, knitted, or other fabric, or film. Other embodiments of the system can enable surface coating of 3D articles that are passed through the system by a conveyor, clamp, fastener, or other holding mechanism. Alternatively, the 3D article can be processed in a fixed location, and the processing head of the system can move to and from article 1 to process the article.

[0049] For example, a single chamber 15 may be provided and used initially to dispense a pigment or particle coating onto article 1, after which the pigment applicator 18 may be moved or otherwise stopped and the plasma treatment device 20 moved into position and / or activated to apply a plasma coating and / or treatment. Optionally, the same treatment module 20 may be configured to provide both dye and / or pigment present in a solution or carrier fluid to article 1 and then plasma treat and / or coat the article 1. The carrier fluid may be, for example, an aerosol, vapor, liquid, or gas. Multiple monomer sources may be present, with selective introduction of fluids from within the sources, as desired.

[0050] In another embodiment, the system 10 can include a chamber 15 for a pigment applicator 18 that can apply a pigment to the article. One or more pigment applicators can be provided, with each applicator 18 configured to apply the same pigment or multiple pigments (which may be unique pigments or colorants). After applying the pigment to the article, the system 10 transfers the article 1 to a localized area adjacent to a plasma module 20, which applies a plasma-formed polymer film or coating to the article 1. During the plasma polymerization process, the article 1 is configured to move continuously under the module 20, thereby applying successive coatings to the article 1. Once the article 1 has moved under the module 20 and received the plasma coating or has a coating polymerized thereon, the article 1 can enter a processing region of a post-processing module. The post-processing module can be used to cure, finish, gloss, matte, or texture the plasma-polymerized coating on the article.

[0051] It will be appreciated that in this embodiment, the system 10 is configured to provide a chemical, monomer, or precursor to the article during application and / or polymerization of the pigment. When both the pigment applicator 18 and the module 20 are adapted to provide a chemical, monomer, or precursor, they may be the same chemical, monomer, or precursor, or different chemicals, monomers, or precursors. Furthermore, regardless of the application device for the chemical, monomer, or precursor, the plasma module 20 is preferably adapted to polymerize or substantially polymerize the chemical, monomer, or precursor provided on the article. The degree of polymerization also depends on the end use of the article; the plasma module 20 can also be adapted to only partially polymerize the chemical, monomer, or precursor that forms the coating on the article 1. This may be particularly useful for pigments that are releasably retained by the article, such as for drug release. A partially polymerized plasma-polymerized coating may also be beneficial for other uses or applications.

[0052] A user terminal 11 may be provided in communication with the system 10 and may be used to input variables, select fluids, monitor one or more chambers, and start and stop processes. Any desired terminal interface may be used, and the terminal may control the operation of one or more components of the system 10. Software may be executed via the terminal and may be remotely updatable. Preferably, a storage medium within the terminal 11 may be used to store data from processing, as well as data related to errors or unauthorized use or access to the system.

[0053] Referring to FIG. 2A, a system 10 is shown including a first processing chamber 15A, a second processing chamber 15B, and a third chamber 15C. It should be understood that all chambers 15A can be combined into a single chamber 15A, or more than one chamber can be used as shown. The first chamber 15A can be a pigment application chamber 15A. Optionally, multiple pigment application chambers can include respective pigment applicators 18 adapted to apply a predetermined pigment or colorant to the article 1. Having separate pigment application chambers can reduce the possibility of cross-contamination of the pigments. If the pigment application chamber includes a spray applicator that applies a dispersion or other liquid to the article 1, the system may include an additional chamber (not shown) including a drying segment. Alternatively, the drying segment can be located within the spray applicator chamber 15A and can include at least one heater or device used to remove liquid from the article before it is exposed to the plasma region. The second chamber 15B may be a plasma processing chamber 15B, and the third chamber may be a post-processing chamber 15C with a post-processing module 21. The post-processing module 21 may include at least one of a heating device, a cooling device, an additional module 20, a plasma device, or a clamping or curing device that can be used to apply additional coatings, finish the polymerization process, or modify the plasma coating applied by the module 20. The chamber 15 is preferably sealable and can form a fluid-tight seal that can maintain a desired local atmosphere. The chamber may optionally have entry and exit points so that a planar article 1 can enter the chamber 15 for processing and be removed from the chamber after processing. The entry and exit points preferably have seals that prevent or substantially reduce the ingress of atmosphere outside the chamber 15. Rollers 60 may be used to transport the article through the chamber 15.

[0054] Each chamber 15 can be adapted for a specific portion of the process, and each chamber 15 can have a distinct pressure, atmosphere, processing module, and / or length. The first chamber 15A can be used to apply pigment to the article 1 via a pigment applicator 18. The pigment can be provided as dry particulates or can be provided in a liquid-borne or dissolved state. If the pigment is applied as a dry substance, the pigment can be sprayed onto the article in a manner that substantially captures the pigment on the surface of the article, or can be imparted with a velocity that penetrates at least partially into the article 1. Pigment penetration can be particularly useful when it is desired to dye or color a textile with a colorant.

[0055] An interlock or airlock may be provided between the first chamber 15A and the second chamber 15B to maintain each chamber in a desired state and substantially free of unmanageable amounts of contaminants (similarly, the third chamber 15C may have such an interlock or airlock). Each chamber used in the system may have an airlock, roller, or fluid control device at its inlet and outlet. Airlocks are preferably used to maintain a desired atmosphere within the chamber and ensure that the desired processing occurs without introducing unknown contaminants into the processing.

[0056] In yet another embodiment, the system does not include airlocks between chambers, in which case chamber 15B is configured to have a relatively higher pressure than the other chambers, thereby forcing gas supplied to chamber 15B toward the other chambers of the system.

[0057] In another embodiment, a high pressure section can be provided between the chambers to supply the chambers with plasma gas or other desired gases, thereby forcing fluid from the high pressure section into the immediately adjacent chamber.

[0058] In yet another embodiment, the system 10 can include a pretreatment chamber preceding the pigment applicator chamber 15A, which may be similar to chamber 15C, except that it functions as a pretreatment chamber rather than a posttreatment chamber. The pretreatment chamber can be adapted to apply a primer to the article 1 to receive the pigment thereon. Alternatively, the pretreatment chamber can be used to activate or modify the surface of the article before the pigment is applied thereto. The primer can be a layer formed by at least partially polymerized HMDSO, argon plasma treatment, nitrogen plasma treatment, or oxygen plasma treatment. It should be understood that any of the reactive gases described above can be mixed with argon or another inert gas in any desired ratio. The reactive species can temporarily bond to the surface of the article and improve pigment adhesion in a subsequent application step. Optionally, rather than using an inert gas, it may be advantageous to mix at least two reactive gases to enhance or modify the properties of the chemicals and / or the surface of the article through the use of reactive gas species.

[0059] Chamber 15 is temperature controlled by the gases injected therein, and the temperature inside the chamber can range on average from 15° C. to 35° C. In this range, the articles being treated can have superior deposition rates compared to temperatures outside this range.

[0060] The temperature of the plasma fluid and / or monomer may range from 10°C to 50°C upon entering the chamber. Excitation from the plasma region may increase the temperature of these fluids, thereby increasing the temperature of chamber 15. Certain chemicals, monomers, and precursors may require temperatures of up to approximately 250°C for vaporization or atomization, and at these temperatures the chamber temperature may exceed these temperatures; however, this is also a potentially desirable embodiment of the system, and the chamber can be adapted to allow processing up to these temperature ranges. That is, the temperature of the vaporized, evaporated, or atomized fluid injected into the plasma region can be the temperature within the chamber, if desired.

[0061] In another embodiment, at least one consumable of the system, such as the carrier gas, monomer, plasma gas, pigment, or solution used in the system, is individually temperature-controlled. Each of these consumables can be temperature-controlled within a range of -10°C to +150°C. Other temperature ranges are possible, as long as they are between the freezing temperature of the consumable and the vaporization temperature of the consumable at the time of introduction into the fluid supply line or plasma region. Increasing the temperature of some consumables can be advantageous because they are more likely to fractionate upon entering the plasma region, resulting in a more durable coating or a coating with desired properties. Additionally, the carrier gas can be adapted to carry a larger amount of at least one of the monomer or pigment by increasing the temperature of the respective monomer or pigment. Alternatively, the temperature of the carrier gas can be increased to further carry the monomer and / or pigment.

[0062] Photoionization (PID) sensors, fluid flow sensors, temperature sensors, or other fluid sensors may be used within the fluid delivery system 40 to monitor and control fluid distribution. The sensors may also be adapted to determine the concentration and fluid extracted from the chamber for recycling in the recirculation system 70, described below. Based on the detected concentration and composition of the fluid extracted from the chamber 15 and injected into the recirculation system 70, the concentration and amount of unused fluid from the fluid source may be varied to create a more uniform mixture. It will be appreciated that the recycled fluid and unused fluid may collectively create a desired concentration that is supplied to the chamber 15. The desired concentration that is supplied to the chamber may be used to form the plasma region and / or the polymerized coating applied to the article 1.

[0063] In another embodiment, the recirculation system can include a reservoir 95, such as a tank or other receptacle. Multiple reservoirs 95 can be provided that can be used to store the separated fluids. For example, a first reservoir 95 can be used to store the carrier fluid, and a second reservoir can be used to store the monomer or partially polymerized monomer. The reservoirs 95 can be used to temporarily store the recovered fluids, which can then be reinjected into the recirculation system 70 or removed for further processing or purification.

[0064] Atomizer 55 can be used to atomize the monomer and pigment that are delivered through the fluid delivery system to reaction gap 110. Atomizer 55 can be located within mixing chamber 50. In this embodiment, module 20 with reaction gap 110 can function as a pigment applicator in addition to a plasma polymerization coating device.

[0065] The mixing chamber 50 can be used to mix pigment and monomer in preset amounts to achieve a desired ratio of monomer to pigment. A syringe or dosing means can be used to inject preset amounts of monomer and / or pigment fluids that are mixed in the mixing chamber 50 and then atomized. The mixing chamber forms part of the fluid delivery system 40.

[0066] The fluid delivery system 40 may also include a plurality of gas pipes 114 or conduits adapted to deliver fluid into the chamber 15. The gas pipes 114 include a plurality of gas outlets 116 that allow pressurized gas to be dispersed within the chamber 15. The gas outlets 116 may supply a pure substance, such as a desired fluid, to the chamber 15. The desired fluid may include at least one of a monomer, a precursor, a chemical, a plasma gas, a liquid, a reactive gas, a Penning ionizable gas, and a sacrificial gas. The gas outlets may also supply at least one of a carrier fluid, a monomer, a monomer mixed with a pigment, and a pigment mixed with a monomer to the chamber 15. The polymerizable monomer and the pigment therein may be immobilized within, on, or under a coating formed on the article 1.

[0067] The gas outlet 116 can inject a fluid so that it forms a stream as it enters the plasma and moves toward the article 1. The plasma gas can be released into the chamber atmosphere before being excited to form a plasma at the electrode 100, thereby forming a non-traditional type of plasma stream. The plasma stream may be similar in appearance to plasma torches known in the art; however, unlike a plasma torch, it should be understood that the plasma stream forms above the excitation region and forms a cold stream of plasma. This is advantageous because the plasma stream is formed by the fluid supply pressure and is adapted to move through a free region above the electrodes before entering the plasma region 112. This allows a carrier fluid to also flow into the region above the electrodes, which can advantageously help smooth the plasma generated between the electrodes 100 or create a more uniform plasma extending across multiple sets of electrodes in the chamber 15.

[0068] The bias plate 120 can be used to attract ionized material, which can help increase the deposition rate or impart fluid motion to the ions. The bias plate is preferably positioned below the module 20 so that particles from the module 20 are attracted to the article 1. The bias plate 120 is powered by the bias power supply 118 or the power supply 30.

[0069] Preferably, the bias plate 120 is a negatively charged DC bias plate. Optionally, instead of a DC bias, an AC bias may be used. It will be understood that the bias plate 120 may be positively charged, if desired. Penning traps may be used above and / or below the plasma region to repel or attract ionized material within the plasma region in a particular direction. Preferably, when a Penning trap is used, the polarity of the Penning trap is opposite to that of the bias plate, if present. A magnetic field may also be used to guide the movement of ions within the plasma region, directing positive and / or negative ions in a desired vector or direction. In another embodiment, the bias plate 120 may be configured as a DC bias plate or an AC bias plate, functioning similarly to an electrode, with the electrode of the module having a uniform polarity opposite that of the bias plate.

[0070] 5A and 5B, an embodiment of a processing module 20 is shown. The module 20 comprises a housing 22 having a plurality of electrodes 100 mounted therein and at least one gas outlet 116. The housing 22 is configured to support the electrodes 100 and the gas outlet 116 of the fluid delivery system 40.

[0071] The outlets 116 may be located within a diffuser plate (not shown) that aids in the dispersion of the carrier fluid and the entrained particles or fluid. In the embodiment shown in FIGS. 5A and 5B , gas conduits 114 are located with gas outlets 116. The gas conduits are located relatively above the electrodes 100. In a preferred embodiment, the gas outlets 116 are located above the reaction gaps 110 between the electrodes 100. In this manner, the gas outlets can focus the gas toward the reaction gaps 110. The number of gas outlets may be the same or fewer than the number of reaction gaps 110, or may be up to two more than the number of reaction gaps. However, it will be understood that the number of gas conduits within a module may be any desired number to enable sufficient delivery of fluid into the electrodes 100 and / or chambers 15.

[0072] The article 1 is shown below the module 20 relative to the module 20 and is configured to pass under the module 20. The article 1 can be coated or treated by passing under the module 20. The first module 20 in the chamber can optionally be adapted to modify functional groups remaining on the surface of the article after pigment application. The functional groups can be modified with any desired plasma gas, preferably an inert gas. Functional group modification can be advantageous because some dispersants that can be used to apply pigments are hydrophilic, and the desired coating may include a durable, water-repellent coating. Modifying residual functional groups may be desirable to remove functional aspects so that subsequent plasma coatings can be applied more effectively to the article. Furthermore, modification can reduce the likelihood that the desired functionality of the plasma coating will be weakened by underlying residual functional groups. For example, modifying a hydrophilic coating to a neutral or non-hydrophilic coating may improve the performance of a subsequent hydrophobic coating.

[0073] Rollers 60 or supports 80 can be used to transport or convey the article from the first side of the module to the second side, with article 1' being the treated article. When the electrodes are energized to maintain a plasma in the reaction gap, the plasma region 112 can extend across multiple electrodes 100, as shown. It will be appreciated that the reaction gap is where the plasma is initially formed, and the plasma region ignites or otherwise excites the atmosphere near the electrodes 100, resulting in a plasma glow. Preferably, the plasma glow is generally uniform across multiple sets of electrodes 100, allowing for a much larger area to be treated or coated simultaneously than is possible with a plasma torch or plasma jet. Furthermore, the plasma region formed by the electrodes is preferably above the article 1 to be coated, so that the plasma need not directly interact with the article 1 unless necessary. Fluids, such as carrier fluid, atomized monomer, monomer vapor, monomer aerosol, and / or pigment, can flow into chamber 15 through outlet 116. The fluid can diffuse outward 124 through the holes, or, under sufficient pressure, form a fluid column 126. The dispersed fluid 124 can be used to spread the fluid across the electrodes 100 and provide regions of different fluid densities. This can assist in the formation of a plasma region 112 that extends across multiple electrodes 100. Alternatively, a column of fluid can be ignited to form a plasma stream. This plasma stream can be used in some embodiments to form a spot coating or a more focused coating. Unlike a conventional plasma jet, the plasma stream is non-thermal and can be injected into the open chamber 15 before reaching the electrode 100 to ignite or excite the plasma fluid. This allows the injected fluid to mix with the local fluid within the chamber 15 before reaching the electrode. This method of forming a plasma can also allow other gases within the chamber 15 that are not exhausted through the outlet 114 to be entrained or collected and carried to the reaction gap 110.

[0074] Optionally, the size of the outlet 116 can be varied by the insertion of a nozzle or other flow direction or flow restriction device. The outlet 116 may include threads or attachment means into which a nozzle may be inserted to vary the type or distribution of fluid flow entering the chamber 15. Nozzles may also be used to direct the flow in a desired direction. The nozzle may also be fitted with a solenoid, restrictor, or closure means to seal the nozzle, if desired. This is particularly useful when multiple coatings or processes are used within the chamber 15, as the outlet can be selectively turned on or off.

[0075] FIG. 4 is a side view of one embodiment of module 20 including a pigment applicator. The pigment applicator can be positioned relatively below a manifold that supplies plasma fluid and at least one of chemicals, monomers, and precursors to the article. In yet another embodiment, pigment applicator 18 can be positioned relatively above the manifold of module 20. The pigment applicator can be multiple tubular sections that can be used to supply liquid and / or pigment to the reaction gap 110 of the plasma region before application to the article. A fluid reservoir can be used to store fluid for the pigment applicator, and the pigment applicator can include a preset dosing or control mechanism to introduce a desired amount of pigment into the plasma region.

[0076] Having a pigment applicator as part of module 20 can have many advantages, particularly the possibility of Penning ionization effects by introducing the pigment into the plasma region. Additionally, the pigment and / or pigment carrier can be used as precursors that are polymerized in the plasma. This is also advantageous in plasma-polymerizing dyes, where one or two chemicals must be mixed, and subsequent plasma polymerization can be used to impart the desired colorant and fix the dye to the article.

[0077] 2A, a pigment applicator is separate from the plasma module and adapted to apply the dispersion to article 1. This can be beneficial as it allows the dispersion to be removed prior to the plasma region generated by module 20.

[0078] Preferably, the dispersion has a high concentration of pigment, which may be at least 30% by weight of the dispersion. More preferably, the weight of pigment in the dispersion may range from 60% to 90% by weight of the dispersion. In another embodiment, the pigment is applied without a dispersant and applied "dry" to the fabric. The system can be adapted to dilute more concentrated dispersions as needed. In this configuration, a predetermined or known amount of dispersion can be mixed or otherwise combined with a fluid capable of dispersing the high-concentration dispersion. This is particularly beneficial for Article 1, which is different from other articles processed in the system. For example, if Article 1 is a cotton substrate, the dispersion can be diluted in a first dilution, and if Article 1 is a polyester substrate, the dispersion can be diluted in a second dilution. Each dilution may depend on the composition of the article, especially for textiles and other substrates. While cotton and polyester are specifically shown, each substrate type may have its own dilution, or similar or the same dilution may be used to apply the pigment to the substrate.

[0079] For dispersions with higher pigment concentrations by weight, the dispersion becomes paste-like and can be diluted as needed. Solvents or water can be used to dilute the paste in system 10, and the diluted paste can then be fed to a spray system for application to article 1.

[0080] Dispersants can be used to dilute the pigment dispersion or to impart desired dispersibility to the pigment dispersion. In at least one embodiment, dispersants such as Tego Dispers 755W (10-200% pigment by weight (wop)), Surfadol XL167 Dispersant (10-50% wop), Disperbyk-199 Dispersant (20-150% wop), Tego Dispers 750W, Lubrizol W150, Convey CT12, and Convey MT02 can form part of the pigment-bearing fluid provided in Article 1. Other commonly used dispersants can also be used in the present disclosure, and the above dispersants are not an exhaustive list. Optionally, a hyperdispersant such as Lubrizol W100 can be used in the range of 20-150% pigment by weight.

[0081] Wetting agents such as Surfadol TG can be used in the range of 10-100% by weight of the pigment. The wetting agent can also be any other surfactant that can improve wetting. Additionally, a leveling agent such as Polyox N12K (PEG 1,000,000) can be used in the range of 0.01-0.1% by weight. Any desired combination of the above can be used in at least one embodiment of the present invention.

[0082] The following are examples of pigment dispersions that can be used in the system: Example 1: 2% weight / volume (w / v) Irgazin Orange with 15% pigment by weight (w / v), TEGO Disperse 755W, and 0.05% w / v Polyox N12K. Example 2: 2% w / v Sicopal Yellow with 3% w / v Lubrizol W100. Example 3: 2% w / v Navamin Carmine with 100% w / v Surfadol TG, 30% w / v Lubrizol W100, and 0.1% w / v Polyox N12K. Example 4: 2% w / v Unifast Blue with 20% w / v Surfadol TG, 20% w / v Surfadol XL167, and 0.05% w / v Polyox N12K. Example 5: 1% w / v black iron oxide was mixed with 100% w / v Lubrizol W100, 10% w / v Surfadol XL167, and 0.05% w / v Polyox 308. Example 6: 1% w / v black iron oxide was mixed with 10% w / v Surfadol TG, 30% w / v Surfadol XL167, and 0.05% w / v Polyox 308. Example 7: 2% w / v Roman black was mixed with 50% w / v Surfadol TG. Example 8: 2% w / v Vine black was mixed with 100% w / v Tego dispers 755W and 0.05% w / v Polyox N12K. Example 9: 2% w / v Prussian Blue with 175% w / v Tego Dispers 755W and 0.05% w / v Polyox N12K. Example 10: 60% pre-reduced indigo (KraftKolor) with 55% w / v Tego Dispers 755W.

[0083] The above examples are not exhaustive and other pigment and dispersing additives may be used, and it may be preferable to minimize additives as this can make the drying or heating process more efficient and reduce the likelihood of reactive species getting into the plasma region generated by the module.

[0084] In another embodiment, the pigment can be dissolved in a solvent and applied to the article with a spray applicator. The solvent can be evaporated by heater segments, thereby depositing the pigment on the surface of the article.

[0085] 5A and 5B illustrate multiple circular electrodes 100 of opposite polarity, where a plasma can be formed between the electrodes 100, such that the reaction gap 110 is the center-to-center distance between the circular electrodes 100. Other electrode cross-sections can be utilized depending on the desired plasma to be formed, the desired coating, or the desired cooling for the electrode or plasma temperature. For example, square, rectangular, oval, or other regular shapes may be desired for the electrodes. A cooling system 45 can be used with the electrode 100 to cool the sheath and / or core temperature to a desired temperature range, which may help reduce damage to the article 1 being treated. The cooling system can be configured to communicate with the fluid channels 108 of the electrode 100.

[0086] A bias 120 may be provided under the article 1 and may be used to attract the article and / or attract fluid from the module 20 toward the article 1. The bias may also be used to impart a visual effect to the plasma region 112. For example, the bias may be used to create a more uniform plasma, which may promote a more desirable coating. The bias may be an electrical bias, such as a DC bias or an AC bias.

[0087] A method for treating article 1 can include providing an article having a generally sheet-like or planar configuration with a polymer formed by plasma polymerization. Article 1 can have at least one fiber or thread exposed to a surface treatable by system 10. The polymer can be formed by a plasma at atmospheric pressure, where the energy of the plasma is sufficient to cause polymerization of the monomer and subsequent bonding of the polymer to article 1. The thickness of the polymer coating applied to article 1 can depend on the density of the plasma, the coating time, and the amount of monomer introduced into the plasma region.

[0088] In another embodiment, the carrier fluid and atomized substance are delivered to the chamber by the delivery system 40 and dispersed within the chamber via a diffuser plate (not shown). The diffuser plate can be positioned above the electrode 100 to more evenly distribute the gas across the electrode 100 at a generally uniform velocity, thereby reducing spot coating that can result from the use of pressurized gas from the gas outlet 116.

[0089] In yet another embodiment, module 20 can be fitted with a series of lasers or other sensors that can identify the location of an article relatively below module 20. Once an article is identified below module 20, electrodes directly above article 1 can be selectively turned on to form the desired plasma. This is particularly valuable because it does not require activating or energizing the entire module 20, and resources such as power, plasma gas, monomers, and pigments can be conserved because they are not supplied to module 20 in areas that are not relatively above article 1.

[0090] In yet another embodiment, a method for depositing a pigment on an article 1 is provided, comprising the steps of atomizing a colloidal solution (or suspension) containing the pigment, introducing the solution into a plasma region, and depositing the pigment on the surface of the article 1 in atmospheric pressure plasma.

[0091] Pigments are aggregates of small molecules or hundreds to thousands of atoms that form particles, with dimensions ranging from 1 nm to 1000 nm, more preferably from about 200 nm to 1000 nm. Larger particles can be carried by a carrier fluid, combined with a monomer, or transported by aerosolization, vaporization, or evaporation of the monomer.

[0092] The power supply 30 may be a generator or other power device capable of supplying power to the system and its components. For example, the power supply may be connected to a processing module within the chamber 15. A cooling system 75 may also be used to cool the system during use, particularly to cool at least one of the processing module 20, the electrode 100, and the bias plate 120. The article may be supported on a support 80, below which a bias 120 may be disposed. The bias may be a DC bias (or an AC bias) or other electrical bias that may assist in controlling the plasma and / or directing the flow of particles from the plasma region 112. This may further encourage the polymerized monomer and / or pigment therein to flow toward and deposit on the article 1.

[0093] The system 10 includes at least one pair of electrodes 100, which can be used to ignite or collide a plasma gas to form a plasma (which may be a dielectric barrier discharge). The space between the electrodes 100 is also called a reaction gap, where a reaction between a voltage and a plasma fluid is observed, or where polymerization or fractionation of a monomer or polymer occurs. Fractionation of the monomer can occur in a plasma region 112, which exists above, below, or between the electrodes, as illustrated in FIG. 5B. After fractionation, molecules formed from the monomer flow in the direction of the jet or in the direction of a local electric or magnetic field, preferably toward the article, whereby the fractionated molecules recombine to form a preferably crosslinked or highly crosslinked polymer, which can then form a chemical or physical bond with the article 1. The plasma region 112 is formed within the reaction gap 110, which can fill the entire reaction gap 110 or a portion of it. The space between the electrodes 100 can range from 1 mm to 12 mm depending on the desired plasma density, and this space can be the reaction gap 110. The spacing between the electrodes 100 may be the sheath-to-sheath spacing of adjacent electrodes 100 or the center-to-center spacing of adjacent electrodes 100. It will be appreciated that when the spacing is sheath-to-sheath, the distance between the cores will be greater.

[0094] A dielectric barrier discharge is typically characterized by the presence of at least one dielectric barrier, e.g., a sheath 104, and a reactive gap 110 located between a pair of electrodes 100. A dielectric barrier discharge can have the ability to break chemical bonds, excite atomic and molecular particles, and generate active particles such as free radicals. Dielectric barrier discharge systems are also referred to as "non-thermal systems," "non-equilibrium systems," or "low-temperature plasma systems."

[0095] In contrast to non-thermal systems, thermal plasmas have electrons and heavy particles at the same temperature and are therefore in thermal equilibrium with each other. However, non-thermal plasmas are typically characterized by the inclusion of ions and uncharged particles (heavy particles) that are at a lower temperature than the electrons. Because the temperature of the heavy particles in the plasma can be kept relatively low, preventing undesired polymer degradation, dielectric barrier discharge burners are said to be suitable for polymerization and deposition processes. A unique advantage of dielectric barrier discharge systems over other conventional thermal plasma systems is that non-thermal plasma conditions can be easily established at or near atmospheric pressure and can also be used for the processing or polymerization of monomers and / or polymers.

[0096] Plasma can be generated by an electrical discharge between electrodes 100, which can excite or ionize the plasma gas to form the plasma. Any predefined method can be used to generate the plasma, including alternating current (AC) excitation, direct current (DC) excitation, low-frequency excitation, RF excitation, and microwave excitation. Each of these methods can be used to generate atmospheric pressure plasma. "Atmospheric pressure plasma," also known as atmospheric pressure plasma, can be a plasma whose pressure is approximately equal to atmospheric pressure. It will be understood that the pressure within chamber 15, even when filled with a desired local atmosphere, will be similar to the pressure outside chamber 15. In at least one embodiment, the pressure inside the chamber is approximately 1 bar to 5 bar, although other pressures greater than 1 bar can also be used.

[0097] Because the plasma module 20 can be used in ambient atmosphere, a carrier fluid for generating a plasma in the reaction gap 110 can be pumped into the region between the article 1 and the module 20 for a predetermined time, and the ambient atmosphere can be evacuated from the region before igniting the carrier fluid to prevent ionization or activation of the ambient atmosphere molecules. The region between the article 1 and the module 20 is also referred to as the “local region.” Purging the ambient atmosphere can also be desirable when the system 10 is used in a sealed chamber to control functional processing characteristics. For example, purging the chamber 15 can be advantageous because it removes oxygen within the chamber 15 that may react with monomeric or polymerized species.

[0098] At least one additional fluid is supplied to the plasma region 112 carried by a carrier fluid or injected directly into the plasma region 112. The additional fluid can typically be used to treat or coat the substrate 1. In one embodiment, the additional fluid is a monomer that can be polymerized by the plasma region and can be used for plasma enhanced chemical vapor deposition (PECVD). Optionally, the additional fluid is supplied to the plasma module 20 by at least one additional inlet. When a carrier fluid and at least one additional fluid are supplied to the module 20, the fluids are preferably mixed with each other in a desired ratio and a known amount of the additional fluid is supplied to the substrate 1 via an outlet.

[0099] The monomer may be injected into plasma chamber 15 as a liquid spray, vapor, or atomized particles, and may assist in the formation of a desired plasma state as the monomer may be adapted to stabilize the plasma streamer or plasma corona state formed in reaction gap 110. Stabilizing the plasma state refers to forming a plasma glow or stable plasma in reaction gap 110. It will be appreciated that the voltage and frequency applied to electrode 100 may also assist in maintaining and / or forming a stable plasma.

[0100] In yet another embodiment, when article 1 is a substrate, the plasma is used to treat only a first side of the substrate, while the second side of the substrate is protected from treatment or can be treated separately with a different coating or treatment process. This allows for selective modification of one side of the substrate. Protection of one side of the substrate can be achieved by applying a film or protective layer to the second side of the substrate or by pressing the second side of the substrate against a surface that does not allow the second side of the substrate to be coated or treated.

[0101] The power supply 30 may include multiple power supply units. The power supplies 30 may be coupled to each module 20, allowing a system user to activate, deactivate, change, or otherwise manipulate the modules 20 for a desired treatment process. Each module in the system may have its own or separate power supply 30 that can be activated as needed. Alternatively, the power supply 30 may be used to power one or more modules and / or components of the system 10. The power supply 30 may be an RF source for charging the RF electrode, or may be an AC (alternating current) or DC (direct current) power supply 30. The electrode 100 may be formed from a core 102 and a sheath 104 that covers the core. The core 102 is formed from a conductive material, such as copper, gold, or stainless steel, and the sheath 104 is preferably a dielectric material, such as glass or alumina. The core 102 is preferably a conductive material that can withstand heating to a temperature below that of the plasma formed in the plasma region. The selected sheath 104 is formed from a dielectric material that can surround or encapsulate the core 102, thereby reducing arcing and helping to stabilize the plasma formed in the reactive gap 110. Optionally, a fluid channel 108, such as an air gap or liquid gap, can be provided around the core 102, which can aid in the cooling and dielectric properties of the electrode 100. For example, air or an inert gas can be used as a cooling fluid that is passed between the electrode core 102 and the sheath 104. In another embodiment, the electrode 100 is provided with one or more fluid cooling channels or cooling channels that are used to cool the electrode 100. Optionally, the core 102 can be provided with fluid channels through which a fluid can be passed to cool the electrode 100.

[0102] The electrode sheath 104 can be rectangular or circular, while the core 102 can be any predetermined shape, which may or may not match the shape of the electrode sheath. For example, the electrode 100 can be a blade-type electrode 100 with a rectangular sheath cross-section, but the core can be circular or another predetermined shape. The fluid conduit can have any predetermined cross-section, including a regular, sinusoidal, or wave-shaped cross-section. While the overall shape of the sheath 104 can define the type of electrode 100 regardless of the cross-section of the core 102, there may be advantages associated with matching the shape of the core 102 to the shape of the sheath 104.

[0103] Because the system functions as an atmospheric pressure plasma system, chamber 15 does not require vacuum pressure to operate. Cleaning, functionalization, and activation of article 1 can be achieved by various plasma treatment methods and exposure to plasma. In atmospheric conditions, functionalization can impart groups including at least one of oxygen, nitrogen, and hydrogen groups. In another embodiment, plasma can be used to etch a surface or modify a surface by removing material from the surface.

[0104] Once the surface is activated, reactive groups are present on the surface and can form excellent bonds with particles that interact with the surface. In another embodiment, the pigment can be activated by plasma either directly by forming physical bonds or by a reaction at the surface of the pigment.

[0105] Contaminants passing between the chambers may be directed towards an extraction location, and each chamber 15A-15C may be fitted with one or more such extraction devices.

[0106] The extraction location may be connected to an exhaust system or a recirculation system 70. If the pollutants are directed to the recirculation system 70, they may undergo a purification process. The purification may include at least one of a combustion stage, a cooling stage, a heating stage, a capture stage, and an exhaust stage. Each stage may be used in combination with another stage or may be performed in any desired manner, and multiple of the same stages may be used in conjunction with a recirculation stage.

[0107] Recovery and recycling within chamber 15 can be achieved through the use of extraction locations. Multiple extraction locations can be located around the system that can be used to draw fluids and by-products that are desired to be removed from system chamber 15. Filtration may be required to separate larger particles from the collected by-products and gases, while smaller particles can be transported further downstream for collection, purification, and / or removal. The filtration stage may be the first separation process in a recirculation system 70 that accepts products such as fluids and particles from one or more extraction locations.

[0108] Preferably, a cryogenic cooling stage is used to freeze off some contaminants and allow the plasma fluid to be reused in the process. The cryogenic cooling stage may be a cryogenic separation process that uses heat exchangers and separation columns to separate argon from other gases and particulate contaminants. Compression of the gas may occur at the inlet of the recirculation system. The recirculated gas inlet stream is cooled and preferably partially liquefied. Separation of nitrogen, oxygen, and argon may be achieved by the cryogenic separation process. In some embodiments, the gaseous nitrogen and oxygen may be reinjected into the system, stored, or released after separation from the liquid argon.

[0109] In another embodiment, additional contaminants can be added to the recycled gas stream, likely capable of combusting or reacting with other impurities within the circulation system. These include oxygen, nitrogen, and / or hydrogen. Preferably, the contaminants removed from the recycled gas stream are water and CO2, but siloxanes, pigments, solvents, solutions, alcohols, and other contaminants can also be captured and disposed of in a desired manner. It will be appreciated that the polymerized chemicals are the primary source of contamination, and that pigments and solvents / solutions from pigment application can also contribute to the contamination. Thus, the by-products of the system are only known when a specific colorant is selected, and the recycling process can be tailored to specific recycling needs. However, it is preferred that at least the purified plasma gas be returned to the system for further processing. Because recovery is not complete, make-up or supplemental plasma fluid can also be included in the recovered plasma gas.

[0110] Furthermore, the purified gas is preferably returned to the system for further processing of articles at the desired temperature. The temperature of the plasma gas, e.g., argon gas, can be in the range of about -30°C to 40°C.

[0111] Multiple extraction locations may be provided within one or more chambers 15, and each extraction chamber may be adapted to filter incoming gases and / or particulates. Gases, particles, and other fluids entering the extraction locations may be fed into a recirculation system 70.

[0112] The pigment applicator in first chamber 15A is preferably any device usable to deliver or apply pigment to an article. The pigment may be dry, in a binder, dispersed in a liquid dispersion, dispersed in a solution, or dissolved in a solvent when applied. Multiple pigments and pigment states may be applied to the article in first chamber 15A. The pigment applicator may be positioned relatively above the article, as shown in FIG. 1, or may be positioned relatively parallel to the direction of movement of article 1, similar to that shown in FIG. 2.

[0113] A vertically oriented pigment applicator can have a trough or extraction location below the pigment applicator that allows fluid to be sprayed vertically from the applicator onto the article 1. Gravity can then assist in moving excess fluid and / or pigment from the applicator that does not adhere to the article to the extraction location. The pigment applicator can spray fluid in any desired manner, including spraying fluid in a relatively straight line, or spraying fluid in an arc or fan pattern toward the article. The pigment applicator can be positioned in any desired orientation as needed, and can be positioned between 1 mm and 500 mm from the surface of the article 1.

[0114] Multiple applicators can be positioned within chamber 15, 15A. Pigment applicators can also be positioned on both sides of an article, such as a substrate, allowing the article to be coated from two directions. Additionally, having multiple pigment applicators allows for multiple types of pigment to be applied simultaneously onto one or more surfaces of article 1, or the same pigment can be applied to both sides of the article, allowing for multi-sided application of the pigment.

[0115] The pigment may be a colorant and / or a functional pigment applied to the article 1. The dye pigment may also inherently include some functionality, if desired. For example, a colorant formed from a metal oxide may also have functionality applicable to antiviral or antibacterial treatments, as is the case with copper oxide.

[0116] Some pigments are corrosion-inhibiting pigments (CIPs), selected for their corrosion resistance, allowing the diffusion of fluids such as water or air to dissolve or partially dissolve the pigment. Some pigments have a high or low pH, which may be beneficial for different environments and their respective corrosion resistance properties. CIPs are preferably formed with metal ions derived from metal cations such as zinc, copper, titanium, brass, strontium, chromium, lead, molybdenum, aluminum, calcium, and barium. Alternatively, pigments may be anions, such as those derived from phosphorus (orthophosphate and polyphosphate), chromate, and borate.

[0117] Another pigment that can be selected is a conductive pigment, which can be formed at least in part from a material selected from the group consisting of copper, iron, silver, nickel, silver-coated nickel, carbon black, multi-walled and single-walled carbon nanotubes, and the like.

[0118] Thermally conductive pigments can also provide electrical conductivity and improve heat transfer, which can be advantageous for flexible products or products where it is desired to transfer heat away from contact surfaces.

[0119] Optionally, the plasma coating formed to secure the pigment to the article 1 can also have conductive properties, allowing the pigment to provide a conductive path or aid in heat transfer. Conductive pigments are typically applied in one or more layers, which may resemble laminates. Each layer of pigment can have its own pigment, filler, binder, and / or particle size. Also, differences between the laminates can impart desired functional properties to the laminate, which may be useful in battery applications.

[0120] Each of the layers can be subjected to a plasma treatment or a plasma coating can be applied to the pigment to build up the layers. Regardless of the number of layers, the overall structure is also called a coating, and is preferably a plasma coating, as the layers or layers are subjected to a plasma treatment.

[0121] Conductive pigments can also be used for electromagnetic shielding and can be arranged in pre-determined patterns or arrays on an article to allow selective conductivity or EM blocking or shielding.

[0122] In another embodiment, the conductive coating can be formed from conductive pigments and a non-conductive resin binder. The binder holds the pigments together, and the conductive filler provides an electrical path. Charges travel through the conductive filler, and if necessary, short-jump through the matrix between the particles.

[0123] The pigments in these coatings are preferably in the form of flakes, plates, tubes, or elongated elements, although any pigment shape can be used as desired. Pigments for these applications can include carbon powder, nickel flake, silver-coated copper flake, and silver flake. Fillers for these coatings may be preferred to be carbon-based, as this is typically a cost-effective filler and allows for conductive, grounding, and EM shielding applications. Silver pigments may be preferred where high conductivity and / or high frequency EM shielding is required.

[0124] In another embodiment, the pigment applied to article 1 can include ferromagnetic powders such as Fe—Co, Fe—Co—Ni, Fe—Co—Co—Ni, Fe—Co—B, Fe—Co—Cr—B, Mn—Bi, Mn—Al, Fe—Co—V alloys, bronze powders, and other alloys of transition metals.

[0125] The pigment bond is preferably a plasma polymerized coating formed by module 20. The plasma polymerized coating may determine the adhesion, durability, chemical resistance, and hand feel of the coating. The polymerized coating is preferably applied such that the pigment applied by the pigment applicator is fixed to the article. The applied coating may also preferably have one or more functional properties generally considered desirable in the electronics, energy storage, and / or clothing industries.

[0126] After application of the pigment to the article 1, the article 1 is subsequently subjected to a plasma treatment module 20. The plasma treatment module 20 may be adapted to polymerize a monomer or precursor that acts as a solution or solvent for the pigment. Alternatively, the plasma module 20 may be adapted to supply the monomer and / or precursor to be polymerized into the plasma region to form a film or coating on the pigment supplied by the pigment applicator.

[0127] The plasma formed by plasma module 20 may be a glow plasma, which can be formed under atmospheric or near-atmospheric conditions. While conventional plasma systems typically require the use of a vacuum chamber to generate the glow plasma, the present system is configured to generate the glow plasma within a range of 95 kPa to 110 kPa. The pressure within chamber 15 is preferably within a range of 99 kPa to 102 kPa, such that the pressure inside the chamber is not substantially different from the external atmospheric pressure, thereby reducing the inflow and / or outflow of fluids into and / or out of the system, respectively.

[0128] The intensity of the glow plasma can be controlled by the flow rates of the plasma gas, Penning ionization gas, Penning ionization chemical, or the voltage applied to the electrodes of the module 20. The electrodes 20 can be arranged in an array that can form a plasma plane or axis, thereby defining the plasma region of the module. Multiple positive and ground electrodes can be used within a single module 20, with the electrodes for generating the plasma spaced 1 mm to 12 mm from surface to surface. A dielectric barrier discharge (DBD) is a discharge between two electrodes separated by an insulating dielectric barrier.

[0129] Preferably, the electrode is formed by a conductive core and a dielectric barrier sheath covering the conductive core. The thickness of the dielectric is in the range of 0.1 mm to 6 mm, and the core of the electrode has a thickness of 0.1 mm to 6 mm. The conductive core may be circular, and the diameter of the core is in the range of 0.1 mm to 6 mm. Optionally, the core has channels formed therein for passing a coolant therethrough to cool the core and sheath forming the electrode.

[0130] Because the treatment of articles such as textiles typically has a limited heat resistance, the plasma temperature is preferably a low temperature plasma, or the plasma has a temperature below about 200° C. at the location of the plasma region where it is likely to interact with the article. Parameters that can be controlled by the system include plasma gas, residence time of the plasma gas and reactive species, flow rate of the plasma gas and reactive species, frequency, power, pressure, ambient temperature, aerosol, vapor, electrode spacing, bias plate, and gas, monomer, and electrode temperatures.

[0131] Module 20 can be powered by an AC RF power source or a DC power source. Different power sources can have different effects on the formation of the plasma, the pulsing of the plasma, and the total energy required to strike and maintain the plasma. Module 20 can include a striking device that allows for a high energy input that can cause excitation of the plasma gas to form the plasma, and then allows for a lower energy input required to maintain a stable or desired plasma. The striking device can be integrated with the power source or attached to the power source. Plasma striking can require 1.5 to 10 times the voltage required to ignite the plasma compared to maintaining the plasma.

[0132] The voltages required for the electrodes are in the range of 20V to 80V for the primary voltage and 1.5kV to 6kV for the secondary voltage. The power required per unit area of ​​the plasma is 0.1W / cm. 2 ~2W / cm 2 Although it will be understood that the overall geometry of the module 20 and electrodes can affect the plasma area and therefore the plasma density, the power output ranges from 500 W to 4500 W per module. It will be understood that the power and voltage required can vary based on the plasma gas and the monomer or precursor being polymerized.

[0133] A pulsed or duty-cycled power supply may be desirable so that the formation of the plasma or the intensity of the plasma can be varied as needed. It may be advantageous to have a duty cycle in the range of 5% to 60% so that active species are formed within the plasma and applied to the article or existing coating or pigment thereon without forming undesirable species during the polymerization step. The plasma module 20 may also be capable of pulsing the plasma intensity, thereby controlling the deposition rate and the deposition species formed within the plasma region before the deposition species are deposited on the article 1.

[0134] An article passing under the first module 20 may receive a coating or lamination. Subsequent modules 20 may be used to provide additional coatings, additional laminations, and / or continuations of the coating applied by the first module 20. Any number of coatings may be applied to the article, and depending on the spacing between modules and / or the spacing between the electrodes of the modules, various layers of coating may be applied, which may be desirable for the durability of the final overall coating applied to the article and may further aid in fixing the pigment to the article 1.

[0135] Optionally, stacking can be achieved by applying a pigment after the application of the plasma coating and then providing a further plasma coating on top of the pigment so that the pigment is positioned between the plasma coatings / films. In this way, the pigment can be encapsulated or relatively embedded within the plasma coating, thereby fixing the pigment in a more desirable position. Any number of stacking layers can be achieved with this system.

[0136] A post-treatment module may be provided in the third chamber 15C, i.e., chamber 15. The post-treatment module may be selected from the group consisting of a heating element, abrasive element, polishing roller, compaction roller, laser, sintering device, radiant lamp, electromagnetic radiation means, and light irradiation device. The post-treatment device may be utilized to enhance or finish the coating applied in the first and / or second chamber.

[0137] Multiple post-processing modules may be located within chamber 15, 15C or may be located outdoors outside the chamber so that inspection can also be performed during the final post-processing step.

[0138] Although post-treatment steps can be applied to the article to finish or enhance the coating, system 10 can be adapted so that module 20 can apply a coating to article 1 to provide a complete or near-complete plasma polymerized coating that provides the desired properties and in which pigments can be fixed without the need for a post-treatment process.

[0139] Plasma coating refers to any coating formed by a plasma, while plasma treatment refers to the use of plasma to modify or enhance the surface of an article or to react with chemicals applied to the article. It will be understood that plasma treatment forms the plasma coating by polymerizing monomers or precursors already on the article, or by polymerizing monomers or precursors that pass through the plasma from the manifold outlet before being deposited on the article 1.

[0140] The plasma module 20 can be formed to include a housing channel in which a supply manifold is disposed, and at least one electrode pair. The housing channel defines an open surface through which plasma gases and / or chemicals are supplied to the article. The electrode pair is preferably disposed near the top of the channel, and the manifold is disposed relatively below the electrodes.

[0141] FIG. 2B illustrates a further embodiment of a system adapted to deliver pigment to an article. The illustrated pigment applicator is configured to dispense or spray pigment in a generally horizontal direction, allowing the article to pass vertically. The illustrated planar article 1 may be a textile substrate. In this configuration, the spray from the pigment applicator can be more concentrated in a narrower area, preventing excess pigment from dispersing over a larger area. Additionally, a first pigment applicator can be provided on a first side of the substrate article and a second side of the substrate article 1. Optionally, a collection tray or similar collection device can be positioned below the applicator 18 to collect excess pigment and prevent it from falling onto the article moving below as it falls due to gravity. The collection tray can be connected to one or more extraction stations for removing the pigment and fluids associated with its application or transport. In another embodiment, the article does not move below the pigment drip or gravity drop location to prevent the article from being accidentally treated with excess fluid or pigment.

[0142] The plasma module 20 may be housed within the chamber 15 or may be exposed to the atmosphere, where a local purge may be performed prior to striking the plasma to ensure high purity plasma gas is excited. The plasma module is preferably adapted to supply chemicals to the article 1 to be polymerized, whereby the pigment applied by the pigment applicator may be fixed by the plasma coating supplied from the plasma module. This method of coating application is unique, providing smaller particles for polymerization compared to conventional methods in which the coating to be polymerized is applied before being sent to the plasma treatment area.

[0143] The method used by the system to apply a polymer coating to an article is preferably a PECVD process. PECVD processes allow for fractionation before a recombined plasma polymer coating forms on the target surface of the article 1. PECVD processes allow for more effective bond scission through fractionation compared to attempting to polymerize an in-situ coating introduced into the plasma for polymerization, allowing for the use of a wider range of chemicals and precursors. Furthermore, a strengthened or improved bond can be formed between the article 1 and the film or coating formed by the PECVD process. Additionally, due to inherent limitations on the thickness of coatings applied in post-polymerization processes, coatings applied by non-PECVD processes are likely to be very thick as a minimum thickness, making it difficult to form a fully or uniformly polymerized coating, and generally forming weak bonds with the article after polymerization. Therefore, PECVD processes may have inherent advantages over traditional coating methods or post-plasma polymerization methods.

[0144] Pre-applying a coating to be polymerized may require higher power transmission to effectively polymerize the applied coating. Furthermore, the thickness of the coating applied using pre-application methods is typically relatively thick compared to coatings formed by plasma polymerization techniques, in which chemicals are passed through a plasma region before being applied to the article. Therefore, compared to plasma treatment modules that polymerize existing chemicals on the article, plasma coating modules can achieve more complete polymerization while consuming less energy.

[0145] 3 illustrates another embodiment showing multiple pigment applicators and multiple plasma treatment modules. In this configuration, a first pigment applicator can apply a first pigment to an article. The article 1 is then processed in a chamber 15 that includes a plasma treatment module 20. The plasma treatment module 20 is adapted to polymerize the coating applied by the pigment applicator and / or provide a polymerized film or coating on the pigment-bearing article to fix the pigment in place. The combination of the pigment and plasma coating is also referred to as a first plasma coating.

[0146] The second pigment applicator may be positioned after the first plasma module 20 and may be used to provide a subsequent pigment on top of the first plasma coating. The pigment may be added to the first plasma coating in the same manner as the first pigment applicator, or may be applied with a different pigment application device or method, such that the first plasma coating may be used to modify the surface of the article prior to treatment to which the pigment is applied. It will be understood that the second pigment applicator may be functionally equivalent to the first pigment applicator and may provide the same pigment application.

[0147] A second pigment applicator can also be used to apply a second colorant, functional pigment, or any other predetermined pigment to the article and / or first coating. The additional pigment can then receive a plasma coating thereon, which becomes the second plasma coating applied to the article 1. The thickness of the second plasma coating can be thinner than, the same as, or thicker than the first coating.

[0148] In particular, if the plasma module is adapted to provide chemicals for the deposition of a second coating, the first coating on the article may allow the second coating to grow or build relatively faster than the first coating, because the first coating acts as a base layer and the additional coating has a faster deposition rate.

[0149] In a further embodiment, the first plasma coating applied to the article can be partially polymerized, whereby the second pigment applicator can apply a pigment that reacts with the partially polymerized coating or that is partially embedded in or penetrates the partially polymerized coating.

[0150] In another embodiment, a system is adapted to apply a pigment and / or coating to a predetermined location on an article, and a second pigment applicator is configured to apply a pigment and / or coating to the same predetermined location or a second predetermined location. In this manner, the system can be adapted to impart various colorants and / or patterns with various functionality. This may be particularly useful for flexible circuits, patterned aesthetics, abrasion resistance, improved grip, or other predetermined or desired pigment applications.

[0151] In another application, the pigment applicator can be replaced by a hot melt applicator adapted to form beads or 3D arrays on the article. For controlled application of elements to an article, a hot melt applicator can be used to melt granules, pigments, pellets, etc. The elements may be used for tactile applications to which a plasma coating is subsequently applied, or the elements may be hardened by plasma treatment. Hot melt elements may be printed onto an article by a hot melt applicator and solidified on the article. The elements may optionally include one or more pigments contained within or protruding from the element.

[0152] The element is extruded from a hot melt applicator and secured to the article as it solidifies. Plasma coating can be used to assist in securing the element. The element can be secured to the article either chemically or by a surface bond with a distinct interface.

[0153] Optionally, system 10 can be adapted for batch processing of articles 1 or for processing of single articles 1. System 10 is adapted for applying a coating to an article that includes a plasma treatment step.

[0154] A process utilizing the system can include applying pigments, powders, or particles to an article. The terms pigment, powder, particle, and nanoparticle are also collectively referred to as "particles," and references to the term "pigment" can optionally be substituted with the term "particles," so that pigments can be read more broadly in the context of particles.

[0155] In another embodiment, the system can be adapted to apply particles in a solution or solvent to the article. The solution or solvent can then be removed from the article, leaving the particles on the article 1. During removal of the solution or solvent, the surface tension of the solution or solvent being removed from the article can cause the particles to move around on the article. Heating, particularly heated airflow or infrared heating, can be used to evaporate the solution or solvent on the article 1, either to hold the particles approximately where they were applied or to force the particles into recesses in the article 1. This can prevent the particles from clumping together or moving to undesired areas of the article 1, thereby improving the distribution of the particles throughout the article 1.

[0156] The article can have an inherent surface charge that can be temporarily altered to facilitate particle adhesion to one or more desired surfaces of the article 1. The alteration of surface adhesion can be achieved by electrostatic fields, magnetic fields, an electrical charge imparted to the article, or by creating a negative charge on the desired surface of the article through friction. The alteration of surface charge is preferably temporary, but can also be sustained throughout at least part of the treatment of the article so that the pigment is temporarily fixed in place before the plasma polymerized coating is formed around and / or on the pigment.

[0157] The pigment applicator of the system can include one or more different mechanisms for distributing and applying pigment onto article 1. The pigment is preferably stored in a reservoir or hopper and directed to the applicator head through a manifold. The pigment can then be distributed onto the article in a variety of ways.

[0158] The dispersion method varies depending on whether the pigment is in a suspension or whether a dry pigment is provided to the article. The dispersion method includes a carrier fluid, such as a gas or liquid, used to transport the pigment to the article. The gas used to carry the pigment may preferably be an inert gas, or a gas that favors plasma polymerization or the formation of reactive species within the plasma generated by the plasma treatment module 20.

[0159] Optionally, a pigment applicator can form part of the plasma treatment module 20, which can pass the pigment and carrier fluid through the plasma before deposition on the article. During this application of the pigment, the pigment can be excited and combined with a binder, chemical, precursor, monomer, or another pigment. When the pigment and carrier fluid are delivered from the pigment applicator outlet into the plasma region, the excitation of the pigment and / or combination with the precursor, chemical, or monomer is achieved.

[0160] It should be understood that the carrier fluid may not form part of the reaction in the plasma region as part of the desired polymerization process, or may be used to react species in the plasma region where deposition on article 1 is undesirable. By-products produced by the system are gases or particles that can be directed to an extraction location in system chamber 15 and recycled or disposed of.

[0161] In one embodiment, a pigment applicator is adapted to apply powder to an article using electrostatic means. In this configuration, pigment fed into the pigment applicator receives an electric current and becomes charged. The charged particles are then sprayed or dispersed through one or more outlets directed toward the article. The pigment is then attracted to the article and fixed in place by a subsequent plasma coating. The pigment fed for this method is a mixture of pigments, with some pigments providing color and others serving a functional purpose. The functional purpose may be a final functionality imparted to the article or a functionality that aids in the electrostatic coating process of the pigment applicator.

[0162] To aid in the coating process, it may be desirable to impart a charge to the article or even to the surrounding area of ​​the article to improve the attraction of the pigment. This can be done by applying a charge to the article or by providing an electric, static, or electrostatic field around the article that can promote attraction to the article. A bed or chargeable element can be provided relatively below the article to impart the desired charge to an area of ​​the article. It may be preferable for the article to be grounded or to have a charge opposite to that applied to the pigment.

[0163] Pigment coatings can utilize pigments formed from polymeric resins that can be combined with at least one curing agent, leveling agent, colorant, flow modifier, or other additive that imparts functional aspects to the coating. The combination of components can be obtained by melting the composition, cooling the melt, and then grinding the cooled combination into a powder (also referred to herein as a pigment). Pigments of this type can be ground to any desired size and preferably include a binder that can react or polymerize upon exposure to a plasma field.

[0164] Unlike conventional powder coating systems, the system 10 and method herein preferably utilize a plasma treatment step in chambers 15 and 15B. The plasma treatment module can be used to cure, react, melt, or otherwise fix the pigment to the article, thereby rendering the pigment colorant visible after plasma treatment. Optionally, the plasma treatment is a plasma coating step in which an additional chemical is applied to the pigment-coated article. The additional chemical can be a chemical suitable for polymerization upon exposure to a desired plasma condition, such as glow plasma, or a chemical adapted to react with at least one additive or curing agent of the pigment applied in the electrostatic application step when exposed to plasma.

[0165] Optionally, after the plasma treatment or coating step, the article and the coating thereon may be subjected to at least one post-treatment step to finish the coating on the article, including at least one of cooling, heating, polishing, laser irradiation, sintering, electromagnetic radiation, and / or light irradiation, which may be performed in the same chamber 15 as the plasma treatment and / or plasma coating, or in a separate chamber 15C.

[0166] The output of the electrostatic means ranges from 5 kV to 100 kV, although in some configurations the output voltage may be reduced depending on the type or size of the pigment.

[0167] The fluid pressure of the electrostatic pigment applicator can range from 0.5 CFM to 20 CFM, depending on the size of the pigment and the distance to the article. Optionally, a series of individual application devices are used across the width of each applicator 18 to selectively apply pigment across the entire article 1. The fluid used to push the pigment from the pigment applicator can be any compressible, pre-defined gas. Such a fluid can be the same as the plasma gas used in the system's plasma treatment step, or it can be a fluid capable of forming reactive species for reaction within the plasma region. For example, the fluid can be nitrogen, air, oxygen, carbon dioxide, or any other desired reactive gas. Alternatively, an inert gas, such as helium, argon, neon, or xenon, can be used. If the inert gas is different from the plasma gas, the inert gas supplied during the pigment application step can be transported into the plasma region of the plasma module, thereby improving the ease of plasma generation during the plasma treatment step.

[0168] Optionally, the article enters a fluidized bed and the heated article passes through a bed of pigment, whereby the heat of the article supplemented by the localized additional heat source of the fluidized bed is sufficient to melt or react the pigment in the bed and adhere it to the article prior to the plasma treatment step.

[0169] In yet another embodiment, the pigment applicator can be a 5-axis applicator, or if the article being treated is more complex, a 6-axis applicator that can apply pigment to the article from any desired direction or any desired distance, which can be advantageous in controlling the flow of particles and the thickness of the applied pigment coating.

[0170] While a fixed head is generally preferred to simplify the handling of the roll-to-roll article being processed, the pigment applicator can be configured to move if it is desired to impart a particular effect to the coating, for example, axial movement of the pigment applicator across the width can leave portions of the article free of pigment.

[0171] The moving pigment applicator can have an outlet that is relatively smaller than the article being treated, thereby controlling overspray or unwanted application of pigment during movement. The pigment applicator outlet can be any predetermined shape, but preferably has a circular, oval, or rounded shape to aid in controlled application of pigment.

[0172] Spray curtains or injector curtains can be used as part of the pigment application process and are also called spray applicators. Spray applicators can be formed from one or more spray nozzles or atomizing devices. The spray applicator can have a series of outlets aligned in a predetermined manner so that a curtain or wall of pigment application spray, aerosol, vapor, or any other propellant, is ejected from the spray applicator. The fluid and / or pigment from the spray applicator has a temperature range of approximately -50°C to 280°C when ejected from the outlet. The temperature range can be limited based on the article being treated to ensure that the article is not damaged during processing. The temperature at the time of ejection can be higher or lower than ambient temperature, but the fluid and / or pigment may cool or warm by the time they interact with the article, resulting in a fluid and / or pigment temperature that is higher or lower than the allowable temperature tolerance of the article being treated. For example, the melting point of polyester is about 260°C and the temperature of the fluid and / or pigment ejected from the spray applicator is about 280°C, but the distance between the exit of the spray applicator and the polyester article can provide the desired cooling so that the temperature of the fluid and / or pigment is below the melting point of the polyester article.

[0173] It will be appreciated that the system may be adapted to limit minimum and maximum temperatures of the pigment applicator to prevent damage to the selected article type prior to processing. Alternatively, the system may have an article inspection identifier that can automatically detect the material being processed and provide dynamic temperature control.

[0174] Additionally, the system may be adapted to determine the thickness of an article, such as a substrate, and adjust the relative position of the surface being processed relative to at least one of the pigment applicator and / or plasma module and / or post-treatment module. Determining the thickness of the article being processed may be done using virtual measurements, where a virtual box is generated to determine the height profile of the article being processed. Such a system utilizes a camera system capable of assessing at least one of the article's height, width, shape, and porosity. Using these measurements, the compression of the inlet rollers may be varied or modified to allow for a desired processing speed while reducing undesirable tension on the article 1.

[0175] If the chamber gases include one or more recoverable plasma gases, purification of the gas may be desirable. For example, argon gas may be desirable to recover and reuse, with by-product contaminants removed from the recovered gas and returned to module 20 for further use at a purity of about 95% or greater.

[0176] Electrostatic transfer drum (ETD) systems can be used with system 10. These ETDs can be used to apply one or more colors in a preset pattern, array, or shape. The ETD is preferably used to transfer one or more colors across substantially the entire width of the article being processed, although some designs or patterns may instead be limited to a preset image that is reproduced.

[0177] The image reproduced by the ETD can be projected onto the photosensitive surface of a xerographic plate to form an electrostatic latent image thereon. The latent image can then be developed to form a xerographic powder image corresponding to the latent image on the plate surface. In this manner, one or more colors can be imparted or transferred, multiple colors can be imparted or transferred, and any desired pattern or shape can be imparted or transferred. The powder image is then electrostatically transferred to a support surface, which is fixed by a fixing device, thereby transferring the powder image to article 1.

[0178] An energization device, or lamp assembly, is positioned toward the xerographic plate and / or article 1. The energization device can have a plurality of individual lamps, which, upon energization, can expose the photosensitive surface of the xerographic plate at the exposure station with an image having associated colors. The plate can be a flexible photoconductive belt assembly. The photoconductive belt assembly can be mounted so that the optical imaging beam of the original or desired image to be applied is continuously projected onto the belt surface. The belt structure preferably includes a material that can be photosensitized prior to exposure to light by a corona-generating device or other charge-imparting device.

[0179] When the belt surface is exposed to a light image, the photoconductive layer in the areas struck by the light is discharged, leaving an electrostatic latent image on the belt. As the belt surface continues to move, the electrostatic latent image passes through a development station. The development station may include one or more devices containing color developing materials used to selectively develop the electrostatic image. The successively developed electrostatic images are then transported by the belt to a transfer station where they are transferred onto an article. After the image on the belt is transferred to the article, the image-bearing article can be treated with plasma or coated with a plasma polymerized coating. Plasma treatment can also form a plasma polymerized coating on the article 1.

[0180] In another embodiment, article 1 is transported to a fusing assembly, where the transferred powder image on article 1 is permanently affixed to article 1. After fusing, the image can be exposed using white light before being transported to module 20 for plasma treatment or plasma coating. It should be understood that the image can include one or more colorants that are transferred to article 1 during processing to impart a desired color to the article. This can be particularly useful in connection with printing an article or applying a substantially uniform color or pattern to article 1.

[0181] The system can also use devices similar to laser printing. These types of devices use static electricity to impart a charge or attractive properties to the article 1 and / or pigment. Static electricity is simply an electrical charge that accumulates on an insulating object, such as a balloon or your body. Oppositely charged atoms attract each other, so objects with opposite electrostatic fields stick to each other. Laser printers use this phenomenon as a kind of "temporary glue." The core component of this system is the photoreceptor, usually a rotating drum or cylinder. This drum assembly is made of a highly photoconductive material that is discharged by photons.

[0182] In yet another embodiment, the system 10 can also include a brush device for forcing or transferring the pigment on the article 1 into deeper recesses in the article surface. The brush device can have one or more bristles or elongated elements for transferring the pigment. Alternatively, the surface of the article can be scraped or a textured abutment means can be used to press against the surface of the article to redistribute the pigment coating to ensure a uniform coating thickness and / or to redistribute the colorant in the pigment coating before it is introduced into the plasma region. For simplicity, the scrubbing means and textured abutment means will be referred to as brush devices, but each can function in a predetermined manner and can be referred to by any of the above names.

[0183] It is also possible to improve an applied plasma coating by moving larger pigments from the upper regions of the article surface into recesses in the article surface. When the pigment is provided to the article with a polymerizable binder, the improved plasma coating results in better embedding or fixation of the pigment fixed by the plasma coating or plasma process. For example, larger pigments provided to the article can be more easily forced into recesses in the article, thereby improving pigment coverage and / or retention.

[0184] By forcing the pigment into the recesses, a defined pattern can be provided with darker areas and upper sections of the article coated with pigment where the pigment is relatively less or not present at all. Using this method, it may be possible to provide the pigment primarily in the recesses of the article, thereby leaving the upper surface areas of the article largely uncoated with pigment. This may also be advantageous when applying two or more pigments, as it allows for control of the coloring in the recesses and / or upper surface of the article.

[0185] The brush device can be used to form a seal or partial seal with the article, thereby reducing the influx of pigment from the coating chamber of the system into the plasma treatment chamber of the system.

[0186] If the coating chamber and plasma chamber are the same chamber, a brush device can be used to divert excess pigment and / or pigment solution from the surface of the article to a collection reservoir, from which the pigment and / or solution can be recycled or discarded if there are contaminants or if there is a mixture of different color pigments. Optionally, a fluid stream or jet can be used to push the pigment out of the recirculation or recycling flow, thereby removing it from the system or collecting it for disposal.

[0187] In yet another embodiment, the system 10 can utilize a duster or sieve to distribute particles evenly on the article. The duster or sieve can be used to apply pigments below a predetermined size to the article. The duster or sieve pigment applicator can be positioned relatively above the article so that application occurs by gravity. In another embodiment, the system can use a fluid flow to direct pigments that fall through the sieve onto the article to be treated with at least one of the pigment and / or plasma polymerized coating. Pigments that are not of the desired size can be ball milled or crushed after recovery to make them large enough for further manufacturing processes. Multiple sieves or dusters can be used to disperse pigments or to filter or separate pigments desired for the application method.

[0188] Optionally, the system can be adapted to first disperse larger pigments onto the article and then disperse smaller pigments after the larger pigments have been applied. This can be particularly advantageous with respect to pigment fixation, as the larger pigments are used to form a base with the article and the plasma coating is provided to bond or fix those pigments to the article, while the smaller pigments are applied and then fixed by another plasma-polymerized coating or at least partially embedded within the first plasma-polymerized coating. This allows the largest pigments to be more completely embedded, and as the coating or binder for the pigments grows, smaller pigments can be added so that the top surface of the coating that is formed is relatively more uniform.

[0189] Dusting the article with pigment also allows the pigment to be dispersed during the drying process, making it easier to collect unused pigment at the extraction location.

[0190] Another method for dispersing particles can include a spray nozzle. The spray nozzle can have a fluid supply for entraining or pushing a chemical from the outlet. The spray nozzle can be a fluid pressure nozzle with a pressure range of 0.8 to 1.4 bar, or a pulse-width modulated (PWM) nozzle, or an atomizer with a pressure range of 0.8 to 1.2 bar for dispersions or other media in which particles are dispersed, suspended, or otherwise dissolved in a solvent. In other embodiments, the pressure of the PWM nozzle or atomizer nozzle can be in the range of 0.2 bar to 3 bar. The spray nozzle outlet can be used to inject a fluid into the article 1 or to provide a controlled release of a fluid. In some embodiments, the fluid can be a dispersion containing at least one pigment. The dispersion can be aerosolized, evaporated, or vaporized, carrying the pigment in droplets that can be ejected from the nozzle. In the case of aerosols, large pigments may not be carried by aerosol droplets below a certain size, so pigments of a predetermined size based on the aerosol droplet size can only be used to apply pigments below the predetermined size. This can be one way to sieve or filter pigments by controlling the droplet size of the aerosol. This can be achieved, for example, by changing the temperature, pressure, or shape during aerosolization. Other aerosol droplet control methods known in the art can also be used for aerosolization.

[0191] The axial velocity of the liquid exiting the spray nozzle can range from 15 m / s to about 160 m / s, while the liquid is at approximately 1 atmosphere and the temperature of the liquid can range from 15°C to 30°C. In some embodiments, the liquid can be jetted from the spray nozzle at a velocity greater than 160 m / s, which may be desirable if the article being dyed is thick or has functional aspects that may repel the liquid from the spray nozzle. It is also possible to vary the velocity to increase or decrease the pigment exiting the spray nozzle. In some embodiments, the liquid velocity can be increased to decrease the pigment. The liquid velocity can be varied throughout the spray, but higher liquid velocity at the time of jetting is expected to result in deeper penetration into porous or woven articles. Deeper penetration may aid in the coloring of multiple sides of an article surface, if desired. Additionally, single-sided liquid jetting allows for the application of a single pigment or colorant to one side of the article.

[0192] In yet another embodiment, the spray applicators in the system may all be of the same type or a mixture of one or more types to allow for the desired application of the pigment or dispersion. Air atomizing nozzles or fluid pressure atomizing nozzles may be utilized for applying the pigment. The pigment may be in a dispersion, applied in a gel, or applied as a dry or relatively dry pigment. A binder may be used to temporarily bind, fix, or adsorb the pigment to the surface of the article 1. The use of dry pigment is herein referred to in some embodiments as applying a fluid, although it will be understood that the fluid may also be a dry fluid.

[0193] The pulse width modulated nozzle can vary the fluid supply, thereby changing the intensity of the applied color. The color intensity can be varied in any desired manner, such as to apply a uniform color to the article 1, or to impart a pulsed, wavy, transitional, or other desired effect to the article. The effect can be an optical effect or a patterned effect. The throughput of the dispersion or solution can be controlled by the system, thereby increasing or decreasing the amount delivered to the article 1.

[0194] The spray nozzle can spray the pigment-containing dispersion or solution toward the article at a preset distance and / or a preset speed. The nozzle pressure or spray speed can adjust the depth of penetration into an article, such as a porous article. The penetration depth may be particularly useful for colorants applied to textiles, woven substrates, or nonwoven substrates. The penetration depth can be at least 20% of the thickness of the article. It will be understood that the penetration depth can also be limited to 50% or less, such that a first side of the article 1 is treated with a first colorant and a second side of the article is treated with a second colorant. Alternatively, the depth of the colorant can be preset to impart a desired effect to the article and can optionally be applied to one or more sides of the article 1. For example, a dispersion with a color pigment can be applied to the article 1 at a depth of 50% of the article's thickness, and a second dispersion can be applied at a lesser or greater depth, thereby imparting a desired color transition, color change, or color effect such as pearlescence, sparkle, or luster.

[0195] The spray applicator is a cassette that can be removed within the system 10 for maintenance or cleaning. The cassette spray applicator can also be loaded with a desired dispersion, paste, colorant, or other material to be sprayed onto the article 1.

[0196] The particles can be dispersed in a solvent or solution such as ethanol or water, or can utilize chemicals that act as binders or parts of binders that react with additional chemicals provided in the plasma polymerization step.

[0197] Solvent inks can include pigments that are dispersed onto the article by the system and carried by alcohol and / or oil. Alternatively, in some configurations, the pigments are carried by water, as in the case of water-based inks, or by another liquid suitable for dispersing the ink. Solvent and water-based inks can evaporate, leaving the colorant on the article 1.

[0198] If the system is adapted to use a dispersion or other liquid to apply a pigment to the article 1, the system may also include a drying segment, which may have a heater. The drying segment may be positioned between the spray applicator and the plasma module to dry or otherwise remove at least a portion of the dispersion, solvent, or other liquid from the article before it is treated by the plasma module or before a plasma coating is applied to fix the pigment in place. The heater of the drying segment is adapted to remove a minimal amount of liquid from the article before it is treated by module 20 of the system 10. It will be appreciated that because the liquid applied by the pigment applicator is preferably not adapted to polymerize in the plasma region, it is preferable that the liquid applied by the pigment applicator be removed before it is exposed to the plasma.

[0199] Particularly useful heaters in this system include ceramic heaters or glass lamp heaters, which can use radiant heat to evaporate solvents or other liquids from articles before they are treated with plasma or coated with plasma. These types of heaters are corrosion-resistant and can operate in plasma gas environments or environments containing evaporated volatiles. The heating element can have at least one extraction region adjacent to the heater configured to remove moisture or evaporated materials from the system 10. The extraction region can have a pressure differential to drive the movement of evaporated liquid or an active intake to remove fluid from within the system. Optionally, fluid collected from the extraction device can be passed through a recirculation system, allowing a cryogenic trap or other liquid removal system to condense the evaporated liquid captured during extraction.

[0200] The heater installed in the system may optionally be provided with a heater shroud to insulate it from other components of the system 10. Additionally, the heater shroud may have an extraction area therein such that the shroud surrounds the heater and the evaporated liquid extraction portion. The clearance below the shroud is sized to allow items to pass underneath and to minimize the inflow of evaporated liquid into the chamber area adjacent the heater shroud.

[0201] As the article passes under the heater shroud, it is cooled by the plasma gas in the chamber to the desired temperature before entering the plasma region. This can be beneficial for certain types of coatings, as it is desirable for the temperature of the article to be within the range of -10°C to 40°C during plasma coating.

[0202] In yet another embodiment, the system 10 can use a padder system to apply a pigment in a solution or solvent to the article 1. The padder system can include an intake roller and one or more mercerizing rollers. The first two mercerizing rollers, forming an inlet pair, are designed as air squeegees, with their gap positioned essentially at the level of the mercerizing liquid. In this way, air is removed from the article as it passes from the air into the liquid, improving the effect of the liquid on the product. The last mercerizing roller abuts the next dye padder roller, which is at least partially intermittently immersed in the mercerizing liquid in the mercerizing vessel. The dye padder roller is designed as a drive roller, on which a squeegee roller is mounted. The squeegee roller can be lifted from the drive roller, for example, rotatably supported on a pivot arm, and the lifting action from the drive roller is achieved by adjusting a lifting means, for example, designed as a pneumatic cylinder. Furthermore, a spray nozzle is mounted approximately at the height of the squeegee roller. These nozzles pre-wash the product during the unwinding of the product in the intermittent mode mentioned at the beginning. A cooling vessel and pump means are further provided below the mercerizing vessel, whereby the intermittent mercerizing process mentioned at the beginning is carried out.

[0203] Optionally, the pigment (which may be a colorant) can be applied to the article in the form of a foam. The foam is generated from a dispersion of the pigment in a liquid or other medium. The foam can expand from the spray nozzle and cover at least a portion of the article being treated. The foam can also be used to more uniformly distribute the pigment in the foam before it contracts, leaving the pigment on the article. The foam applied to the article can also be forced in a desired direction by restricting the volume of the chamber toward an airlock or roller. This can result in a desired or uniform foam thickness on the article prior to plasma treatment.

[0204] In yet another embodiment, the system can be adapted to apply pigments or powders to the substrate. The pigments applied to the substrate can be applied using at least one of electrostatic powder coating (or pigment coating) spraying, drum transfer, dusting, spray nozzle, padding, foam applicator, anilox roller, and printing. Other methods are also applicable and can be described herein.

[0205] Pigments and powders suitable for use in the present disclosure may range in size from 1 nm to 900 microns. Preferably, any pigment or powder used has a thickness within the range of 10 nm to 1000 nm, or within the range of 200 nm to 1000 nm, or within the range of 400 nm to 600 nm, or in some cases an average size within the range of 1 nm to 200 nm. When referring to pigment size, it is understood that the size refers to the size of the material in a single plane only, and that pigments, powders, and particles may have a plate-like geometry or other desired geometry for a particular application.

[0206] For example, mica particles or pigments having a thickness of 1-10 nm but a width at least an order of magnitude greater than the thickness can be used. Plate-like pigments or particles can be randomly oriented when applied to a substrate, or can be urged to lie approximately parallel to the surface of the substrate.

[0207] The color selection for the system can be similar to traditional printing methods employing monochrome to hexachrome color methods, and in some embodiments, heptachrome color methods can be used. Pigments, dyes, or other colorants can be used to provide each color depending on the method used. Colorants can be applied in one or more application processes, and individual pigment applicators can be used to provide different colors, or one or more pigment applicators can be used to provide one or more colorants as needed.

[0208] In another embodiment, pigments that are color-imparting pigments can provide an article with a CMYK (cyan, magenta, yellow, and black) color array. The CMYK coloring of the article uses halftoning or screening, which allows for less than full saturation of the primary colors. This method allows for the use of small dots of each primary color printed in a predetermined manner to provide the desired visual coloration.

[0209] System 10 can be adapted to allow premixing of colorant pigments to form a desired colorant for application to article 1. In another embodiment, it may be desirable to apply the pigment in stages, using a first pigment application module to apply a fixed pigment or pigment mixture to article 1, followed by a second pigment applicator to apply a second pigment or pigment mixture to the article. Three or more pigment applicators can also be used in this manner, each configured to apply one or more preset pigments to the article. In this manner, the application of multiple pigment colorants can provide a desired pigment having the desired colorant. In a further embodiment, a pigment applicator corresponding to one of the colorants for the CMYK process can be provided, resulting in four pigment applicators being used in the process. Similarly, any number of pigment applicators can be provided in the system, each corresponding to a separate colorant for a color process, from a monochrome process to a heptachrome process. In addition to any number of applicators typically required for a preset color process, system 10 can further include a white pigment applicator along with any other pigment applicators. That is, for a heptachrome configuration, approximately eight pigment applicators 18 may be desirable. Multiple pigment applicators may be aimed at the same location on the article simultaneously, such that application by two or more spray applicators occurs simultaneously. It will be understood that the pigment applicator may also be a spray applicator.

[0210] The colorants can be controlled by adjusting the pigment loading on the article or by including white or lighter pigment colorants that enhance or change the intensity or overall visual intensity of the colorants applied to the article. Each of the colorants applied to the article can be applied in a preset amount or weight. The system controller 11 can be configured to dispense the correct amount or loading to achieve the desired colorant on the article.

[0211] In yet another method, the system can also use spot color printing, where specific colorants are used to create colors on the article 1. A spot color or solid color is a color (pure or mixed) that can be produced by inks, pigments, or other colorants and is applied to the article in one go. On the other hand, a process color is created by printing or applying a series of dots of various colors to produce the desired color that is discernible by the viewer. The dots can be applied as pigments that are printed, sprayed, or deposited onto the article 1. The CMYKOG method can utilize a color array similar to CMYK, but additionally includes orange and green colorants that can be used to provide clearer and more accurate colors compared to the CMYK method.

[0212] Optionally, the Pantone™ color system, a six-color hexachrome system, CMYKOG, can be used, which greatly expands the available color gamut. However, it should be understood that other hexachrome systems, such as the CcMmYK color system, which also includes light magenta and light cyan colorants, can also be used. CMYK often cannot produce bright, saturated colors, and bright colors generally make halftone patterns more visible. Using the CcMmYK process, which adds light cyan and magenta inks to CMYK, can solve these problems.

[0213] Although several example color systems have been described, it should be understood that the system can be adapted to utilize one or more other color systems that are standardized or common within the industry. For example, the system can be configured to use at least one of Pantone™, Toyo™, DIC™ Color System Guide, ANPA™, GCMI™, HKS™ (Hostmann-Steinberg Druckfarben, Kast, Ehinger Druckfarben and H. Schmincke & Co.), and RAL™.

[0214] The RAL CLASSIC™ color system is primarily used for powder coating colorants and has a classification system desirable in various industries. Because each system is designed independently, it is understood that a color from one colorant system may not be able to be produced in a second colorant system. However, the system can be adapted to accommodate pigments or other colorants that are compatible with multiple colorant systems.

[0215] Because pigments may be needed infrequently, or some pigments may be used less frequently than others, the system may have one or more devices that can agitate, mix, move, or sonicate the pigments before applying them to article 1. This may result in a more uniform final colorant being applied to article 1.

[0216] The pigments are optically evaluated for their average color, and the system 10 can be adapted to dynamically adjust the final colorant by mixing the pigments in a pre-set manner, which can be similar to conventional printing methods.

[0217] Similar to conventional laser printing devices, pigment applicators can be adapted to apply colorant in a predetermined manner to create a predetermined color pattern or image. Multiple toner and developer units can be mounted on a rotating shaft or wheel. In this way, the printer can apply an electrostatic image for one color and align the toner in the desired location. It can then apply that color, move the next required color into position, and repeat the process as needed.

[0218] Alternatively, all of the colorant can be added to the plate before transferring the image onto the article. Some methods of applying pigment to an article may be limited based on the shape, thickness, or form of the article.

[0219] Natural pigments include plant pigments such as chlorophyll, anthocyanins, carotenoids, and betalains. Natural pigments also include biological pigments selected from the group consisting of heme / porphyrin systems, chlorophyll, bilirubin, hemocyanin, hemoglobin, myoglobin, luminescent luciferin, hematochrome (algal pigment), carotenoids and their derivative mixtures, carotenes, alpha- and beta-carotene, lycopene, rhodopsin, xanthophylls, canthaxanthin, zeaxanthin, lutein, proteinaceous materials, phytochromes, phycobiliproteins, cittacofulvin, thuracin and turacoberdin, melanins, urochromes, and flavonoids. Additionally, algal pigments are suitable for inclusion in plasma coatings. These pigments include chlorophyll a and b pigments and chlorophyll c, phycobiliproteins, phycoerythrin, xanthophyll, and fucoxanthin pigments. Biosynthetic dyes may also be used, whereby bacteria, sugars or other organic matter may be used to produce the desired colorant or pigment.

[0220] Some pigments can be added to coatings with selective color absorption. Such pigments can be synthesized or derived from biological structural pigments such as plant pigments, flower pigments, chromatophores, etc. Additionally, polymerizable chemicals, monomers, and precursors can be generated from biomass sources to produce films or plasma polymerized coatings.

[0221] Bioplastic precursors can be sourced from biomass sources such as vegetable oils, corn starch, straw, wood chips, sawdust, recycled food waste, and seaweed. Some bioplastic precursors are directly processed from natural biopolymers, including polysaccharides (e.g., starch, cellulose, chitosan, and alginate) and proteins (e.g., soy protein, gluten, and gelatin). Other bioplastic precursors are chemically synthesized from sugar derivatives (e.g., lactic acid) and lipids (e.g., fats and oils) obtained from plants and animals, or biologically produced by fermenting sugars and lipids. Materials such as biobased polyethylene terephthalate, biobased polyethylene, and degradable bioplastics, e.g., polylactic acid, polybutylene succinate, and polyhydroxyalkanoates, can be produced from these precursors and other biomass sources. These materials can be used, among other things, as monomers, precursors, or plasma-polymerizable coatings.

[0222] Polysaccharide-based bioplastics are suitable for coating articles with this system, including starch-based plastics, cellulose-based plastics, chitosan, and alginate. Chitosan may be particularly advantageous because pigments and other biopolymers can be easily incorporated into the polymer formed from it, allowing for use in a wide range of packaging applications.

[0223] Starch-derived bioplastics have properties that depend on their amylose / amylopectin ratio. With regard to mechanical properties, pigments may benefit from a higher ratio of amylose starch to amylopectin. Mechanical property ratios are known in bioplastics manufacturing and are incorporated herein by reference. Starch-based bioplastics can optionally be mixed or blended with biodegradable polyesters to produce starch / polylactic acid, starch / polycaprolactone, or starch / polybutylene adipate-co-terephthalate (commonly referred to as Ecoflex™). However, while the above starch bioplastics can be formed with the present system, the present system is particularly advantageous for forming starch-based films suitable for food packaging purposes, wrapping, packaging, paper, and compostable articles. These films can be formed from pigments containing starch and thermoplastic polymers.

[0224] Another type of plastic that can be formed during the plasma polymerization process is protein-based plastics. These plastics can be formed from gluten, casein, and soybeans. Aliphatic biopolyesters are primarily polyhydroxyalkanoates (PHAs), such as poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV), and polyhydroxyhexanoate (PHH). Furthermore, polylactic acid (PLA) can be easily produced in pigment, powder, and granular forms. PLA bioplastics can be used to form films, fibers, and packaging materials, for example. Polyhydroxyalkanoates are linear polyesters produced in nature by bacterial fermentation of sugars and lipids. Polyhydroxyalkanoate monomers can be easily used to form articles suitable for medical purposes. Polyamide 11, polyhydroxyurethanes, lipid-derived polymers, and other biomonomers and / or bioprecursors can be used in this system and can be provided in liquid or pigment form depending on the application method.

[0225] Bio-based polyethylene can be formed from ethylene monomer, which can be derived from ethanol. Other alcohols may also be suitable for forming polymers when exposed to plasma. This may be particularly advantageous when it is desired to carry pigments in the aerosol or vapor, as the liquid portion of the aerosol or vapor may be ethanol or ethylene monomer.

[0226] Generally, there are several categories of pigments, including white pigments, colored pigments, black pigments, and specialty pigments. They may be naturally occurring, synthetic, or a combination of both. Particles that are insoluble in the application medium (varnishes, synthetic materials, printing inks, cosmetic formulations, and building materials) can also be used to form part of the coating.

[0227] White pigments can impart color to article 1 by diffuse reflection of light. Absorption pigments can impart color by absorbing light (additional diffuse reflection). Metallic pigments can produce luster from light reflection and can be metallic pigments. Special effect pigments, such as pearlescent pigments, can impart color, luster, and / or interference effects by reflecting and refracting light (interference). The properties of these pigments can be enhanced by plasma coatings on and / or under the pigment to achieve the desired effect.

[0228] Specialty pigments can include transparent pigments, functional pigments, and effect pigments. Effect pigments can be further divided into two subcategories, including metallic effect pigments and special effect pigments. Metallic effect pigments can preferably include aluminum and / or copper-zinc alloys, and special effect pigments can be used in pearlescent pigments and interference pigments.

[0229] Although pigments may be described herein as having a generally uniform diameter or size, it is understood that this is for simplicity's sake and that pigment surfaces are generally irregular or have uneven surfaces due to their manufacturing process. Pigments suitable for the application methods and systems of the present invention range in size from 0.1 μm to 200 μm in diameter. However, effect pigments may be larger than pigments used simply as colorants. Effect pigments may have a size or diameter ranging from 5 μm to 100 μm, and have the additional property of being transparent, translucent, or light-opaque platelet-like particles. Pigments may also impart other effects, including one or more functional properties such as magnetism, corrosion resistance, luminescence, antibacterial properties, antiviral properties, flame retardancy, hydrophobicity, hydrophilicity, self-cleaning properties, and oleophobicity.

[0230] Effect pigments are generally divided into two categories: metallic effect pigments and special effect pigments. Both metallic effect pigments and special effect pigments produce a lustrous effect on the pigment surface from the reflection of light off the pigment. In special effect pigments, pearlescence and interference occur due to the splitting of light from a beam of light that strikes the pigment surface. This is because only a portion of the light is reflected, while another portion of the light penetrates into transparent or translucent particles, reaches a deeper boundary layer, and is reflected from there. This results in interference, as light waves overlap and are strengthened or weakened depending on their wavelength.

[0231] By selecting metal oxide pigments in relation to the refractive index of the binder (plasma-polymerized coating) and the thickness of the plasma-polymerized coating, various types of color interference phenomena combined with gloss effects can be created. The thickness of these coatings preferably ranges from 5 nm to approximately 500 nm. By varying the size of the pigment particles, various effects can be achieved, ranging from silk matte to highly glossy transparent to opaque finishes. This type of pigment application can use a sieve pigment application method, where the pigment size is controlled, or a combination of pigment application and layered plasma-polymerized coating can be used to achieve the desired effect.

[0232] Pigments can be selected based on their refractive index relative to the thickness of the plasma-polymerized coating and / or the opacity of the plasma-polymerized coating. By evaluating these properties, bright interference colors or interference pigments can be applied to articles. In contrast, metallic luster results from the simple reflection of light from the metal plate. This interaction uses visible light, which is the basis for special effect pigments and metallic effect pigments.

[0233] Any predetermined pigment can be used in the plasma polymerized coating. At least one of a colorant or a functional pigment can be included in the plasma polymerized coating.

[0234] In yet another embodiment, pigments are provided during or before polymerization to aid in coating formation and deposition rate. Surface pigments can improve coating thickness and / or coating adhesion because the polymerized chemicals are more easily trapped on the surface of the article. This is particularly advantageous when chemicals, monomers, or precursors are delivered to the article through a plasma region.

[0235] In another embodiment, the particle size of the pigment can range from 10 nm to 1000 nm, although a more specific particle size may be desirable based on the desired range of pigment optical effects. For example, some pigments may be desirable in the range of 300 to 450 nm to achieve the desired gloss, opacity, transparency, or embedding within the coating.

[0236] Many natural pigments suitable for dyeing purposes exist and can be subjected to a plasma coating or plasma treatment step. The pigments can be embedded in a coating that is applied during the plasma polymerization step or polymerized in a step after the plasma polymerization. Natural pigments can be obtained from natural sources, including, but not limited to, plant roots, nuts, fruits, vegetables, and flowers. Carbon-recovered pigments recovered from industrial emissions or other CO2-emitting sources can also be used.

[0237] Other pigments may be derived from recycled materials, including recycled clothing pigments, recycled plastics, recycled packaging, recycled glass, etc. It is also possible to use other pigments obtained from recycled sources.

[0238] In a further embodiment, mica can be used as a pigment included within the coating. Mica is a commonly naturally occurring mineral that can incorporate a desired sheen into its color. Furthermore, mica pigments can be provided in any pre-set size or desired color and have a generally flat or plate-like appearance. Mica pigments can be provided in sizes ranging from 10 μm to 100 μm across the surface, with thicknesses ranging from 200 nm to 10 μm.

[0239] It may be desirable to include mica pigment because plasma coatings can range in thickness from 100 nm to 500 μm, depending on processing time and parameters. Thus, the thickness of the mica can be oriented relatively parallel to the surface of the article to which it is coated and can be relatively encapsulated or largely embedded within the plasma-polymerized coating.

[0240] Generally, mica pigments can be selected based on their opacity, transparency, and / or luster. As a guide, mica particle sizes of 15 μm or less result in low luster and high opacity; sizes between 2 and 25 μm result in silky luster and high opacity; sizes between 10 and 60 μm can have a pearlescent luster with medium to moderate opacity; sizes between 10 and 125 μm result in a shimmering luster and low opacity toward transparent; sizes between 20 and 150 μm result in a shimmering luster and nearly transparent; and sizes between 45 and 500 μm result in a more shimmering luster and very transparent. The plasma coating used to secure these pigments can also affect the luster and opacity / transparency of the pigment. For example, plasma coatings can be tailored to reduce the luster of pigments with a natural or inherently high luster, thereby making the pigment appear less glossy. Additional functionality can also be imparted by specific pigments embedded, encapsulated, or otherwise bonded in the plasma coating.

[0241] Other metals and inorganic materials that can be used as pigments include titanium, aluminum, zinc, gold, cesium, copper, calcium, strontium, and barium sulfates, zinc sulfide, copper sulfide, titanium dioxide, and barium zeolites, mica, talc, kaolin, mullite, and silica. Furthermore, lead and mercury compounds can also be used depending on the application. The average diameter of the deposited metal can be in the range of 0.01 to 200 microns, preferably 5 to 100 microns.

[0242] The textile to receive the metal coating may be inorganic particles having a first coating of a metal or metal compound and a second coating layer of silica, silicate, borosilicate, aluminosilicate, alumina, or mixtures thereof.

[0243] The inorganic particles, or core material, may be any of the oxides of titanium, aluminum, zinc, copper, calcium, strontium, barium, and lead. Optionally, as suggested, the material may be a sulfide or sulfate. It is preferred to use near-pure metals or metal alloys to form the pigments of the pathogen-disintegrating layer. However, it will be understood that other compounds, such as silver nitrate (AgNO3), titanium dioxide (TiO2), and the like, may also be used. Other pigments commonly used in industry, including organic and inorganic pigments, may also be used, if desired.

[0244] In one embodiment, the pigment can form at least a portion of a continuous coating or film that can conform to the general surface topography of the substrate 10. The pigment can be protected, covered, or have a functional coating applied after deposition that can help reduce the pigment from detaching from the substrate 10. The functional coating properties include at least one of flame retardancy, UV absorption, self-cleaning, hydrophobicity, hydrophilicity, and / or antimicrobial properties. Other functionalizations can also be added as known in the art.

[0245] In other embodiments, the pigments can be suitably formulated in a suitable carrier, coating, or solvent, such as water, methanol, ethanol, acetone, water-soluble polymer adhesives such as polyvinyl acetate (PVA), epoxy resins, polyesters, as well as coupling agents, antistatic agents, etc. Solutions of biological materials, such as phosphate-buffered saline (PBS) or simulated biological fluid (SBF), can also be used. The concentration of the pigment in the solution can range from 0.001% (wt) to about 20% (wt). The pigments can then form a coating that can be applied to the substrate 10.

[0246] Flame retardants can reduce or inhibit the flammability of textiles by reducing the heat release during the combustion process, reducing flammable volatiles, modifying the pyrolysis reaction, forming an intumescent char layer, releasing water, releasing species such as chlorine and phosphorus that act as inhibitors in the gas phase, etc.

[0247] Particles suitable for use in the flame retardant coating can include particles selected from the group consisting of nanoclays, zinc borate, carbon nanotubes (CNTs), layered double hydroxides (LDHs), polyhedral oligomeric silsesquioxanes (POSS), silicon dioxide (SiO2), and metal pigments. Optionally, the SiO2 can be nano-sized. Any combination of particles can be utilized within a single coating. Optionally, the coating can be formed from multiple layered layers.

[0248] Suitable nanoclays may be layered mineral silicate pigments, which, depending on their chemical composition and morphology, can be divided into several classes, such as montmorillonite (MMT), halloysite, etc. Metal pigments may also be metal-based pigments or oxides, such as titanium dioxide (TiO), zinc oxide (ZnO), aluminum oxide (AlO).

[0249] It may be preferred that the thickness of the applied coating is at least 100 nm. For flame retardant treatments or coatings, it may be more preferred to select a coating in the range of 100 nm to 100 microns.

[0250] Preferably, the char yield of the substrate is improved by including a flame-retardant coating. The coating can preferably include particles, such as microparticles or nanoparticles. Char yield testing after application of the coating preferably shows an improvement of at least 1% increase in char yield compared to a substrate that has not been treated with the coating.

[0251] The coating thickness can be in the range of 50 nm to 900 microns. It may be more desirable to provide a coating in the range of 150 nm to 900 nm. Preferably, the coating thickness to particle size ratio is in the range of 1:1 to 1:500, more preferably in the range of 1:2 to 1:200. It will be understood that the average coating thickness is related to the diameter of the particles within the coating.

[0252] It may be preferable for the particles in the coating to be approximately uniform in diameter or size. A particle size distribution may also be provided in the coating, and this distribution may include particle sizes within a known size range, with the remaining particles being larger or smaller than the known size range. For example, 80% of the particles in the coating may have a known particle size by volume, with the remaining 20% ​​being smaller or larger than the known particle size range. In another example, 80% of the particles in the coating may have a known particle size by weight, with the remaining 20% ​​being smaller or larger than the known particle size range.

[0253] Optionally, the applied particle coating provides a flame retardant coating or can be used in combination with a flame retardant coating applied by a chemical vapor deposition process, preferably a plasma enhanced chemical vapor deposition process.

[0254] Particles for flame retardant coatings may be applied to the coating stack or distributed uniformly throughout the coating, or may be deposited on the surface of the substrate to be coated with the functional coating or applied simultaneously with the application of the functional coating to the substrate.

[0255] The thickness of the coating, or the buildup of the coating at the contacting edges of the particles, is preferably sufficient to embed or secure the particles in the desired position. The thickness of the coating may extend over at least 5% of the particle height. Preferably, the particles are encapsulated by the coating.

[0256] Precursors that provide functional properties can optionally be used to complement the pigment selection or to provide a functional binder for the pigment, thereby avoiding or otherwise limiting other post-processing functionalization steps to reduce downstream resource consumption.

[0257] System 10 can be used to deposit a variety of polymer coatings, polymer films, pigment coatings, and pigment treatments onto article 1. Non-limiting examples of coating monomers include acetylene, ethylene, isoprene, hexamethyldisiloxane (HMDSO), tetraethyloxysilane (TEOS), tetraethyloxysilica, orange oil, tea tree oil, peppermint oil, ethanol, butanol, lactic acid, ethyl acetate, gamma-valerolactone, silane (dihydrolevoglucosenone), epsilon-caprolactam, ethyl lactate, stearic acid, candelilla, carnauba wax No.1 Yellow, beeswax, diethyldimethylsiloxane, 1,3-butadiene, styrene, methylstyrene, tetrafluoroethylene (TFE), methane, ethane, propane, butane, pentane, hexane, cyclohexane, acetylene, ethylene, propylene, benzene, isoprene, hexamethyldisiloxane, tetraethyloxysilane, tetraethyloxysilane, diethyldimethylsiloxane, 1,3-butadiene, styrene, methyl methacrylate, tetrafluoroethylene Benzene, pyrrole, cyclohexane, 1-hexene, allylamine, acetylacetone, ethylene oxide, glycidyl methacrylate, acetonitrile, tetrahydrofuran, ethyl acetate, acetic anhydride, aminopropyltrimethylene, triethoxyethane, triethoxyethane, ethoxyethane, ethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane Triethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethaneethoxyethane, triethoxyethanoethoxyethane, triethoxyethaneethoxyethane, triethoxyethanoethoxyethane, triethoxyethaneethoxy, triethoxyethanoethoxyethane, triethoxyethaneethoxy, triethoxyethanoethoxyethane, triethoxyethaneethoxy, triethoxyethanoethoxyethane, triethoxyethaneethoxy, triethoxyethanoethoxyethanol, tricarbonyl(cyclooctatetraene)iron, dicarbonyl The polymerizable composition may contain at least one monomer selected from the group consisting of di(methylcyclopentadienyl)iron, dimerdicarbonyl(dicyclopentadienyl)iron, cobalt cyclopentadienylcobalt acetylacetonate, nickel acetylacetonate, dimethy-(2,4-pentanedionate)gold(III), nickel carbonyl, iron carbonyl, tin acetylacetonate, indium acetylacetonate, and indium tetramethylheptanedionate.

[0258] It may be desirable to remove moisture from the article before applying the plasma treatment or coating. Alternatively, oil can be used to disperse the colorant on the article, and the oil can be polymerized to fix the colorant to the article.

[0259] The oils that can be used are preferably bio-based oils, but synthetic oils can also be used if desired. Bio-based oils include coconut oil, olive oil, sunflower seed oil, shea butter, jojoba oil, almond oil, grape seed oil, rosehip seed oil, orange oil, allspice oil, ambrette seed absolute, amyris oil, angelica root oil, anise oil, anise, star oil, anthopogon oil, Atlas cedarwood oil, balsam fir oil, balsam, Peruvian oil, basil oil, holly oil, bay oil, bay laurel oil, beeswax absolute, benzoin absolute, bergamot oil, bergamot mint oil, black pepper oil, black spruce oil, blood orange oil, blue cypress oil, blue tansy oil, boreal rose oil, boronia absolute, versa grey borense oil, cade oil, cajepat oil, camphor, white olive oil, cananga oil, cannabis oil, caraway seed oil, cardamom oil, carrot seed oil, cassia oil, and kimchi. Chatnip oil, Cedarwood, Atlas oil, Cedarwood, Virginian oil, Chamomile, German oil, Chamomile, Roman oil, Chocolate peppermint oil, Cilantro oil, Cinnamon oil, Cistus oil, Citronella oil, Clary sage oil, Clove bud oil, Coffee oil, Common sage oil, Copaiba balsam oil, Coriander oil, Corn mint oil, Cubeb oil, Cumin oil, Hinoki oil, Japanese cypress oil, Hinoki blue oil, Japanese cypress oil, Irish, Cypress, Taiwan (Formosa) Oil, Davana Oil, Dill Oil, Dalmatian Sage Oil, Douglas Fir Oil, Elemi Oil, Eucalyptus Globulus Oil, Eucalyptus, Lemon Oil, Eucalyptus Radiata Oil, Fennel Oil, Fir, Balsam Oil, Fir, Douglas Oil, Fir, Siberian Oil, Fir, Silver Oil, Fragonia Oil, Frankincense Oil, Galbanum Oil, Geranium Oil, Geranium, Rose Oil, Germanic Chamomile Oil, Greenland Moss Oil,Ginger oil, Goldenrod oil, Grapefruit oil, Guljum balsam oil, Helichrysum gymnocephalum oil, Helichrysum italicum oil, Hemlock spruce oil, Hemp oil, Cypress oil, Hinoki cypress, Taiwan cypress oil, Holy leaf oil, Ho wood oil, Holy basil oil, Hong quai oil, Hop oil, Hyssop oil, Isipingo oil, Immortelle oil, Cypress oil, Jasmine absolute, Jatamansi oil, Java pepper oil, Juniper berry oil, Canucao Iru, Kunzea Oil, Labdanum Oil, Ledum Oil, Laurel Leaf Oil, Lavandin Oil, Lavender Oil, Spike Oil, Ledum Oil, Lemon Oil, Lemon Balm Oil, Lemon Eucalyptus Oil, Lemongrass Oil, Lemon Myrtle Oil, Lemon Tea Tree Oil, Lemon Verbena Oil, Lime Oil, Linden Blossom Absolute, Mandarin Oil, Manuka Oil, Marjoram Oil, Mei Chang Oil, Melissa Oil, Myrrh Oil, Myrrh, Sweet Oil, Myrtle Oil, Myrtle, Lemon Oil, Nard Oil, Neroli Oil, Niaouli Oil, Nutmeg Oil, Oakmoss Absolute, Ocotea Oil, Olibanum Oil, Opoponax Oil, Orange, Bitter Oil, Orange, Blood Oil, Orange, Sweet Oil, Oregano Oil, Palmarosa Oil, Palo Santo Oil, Parsley Oil, Patchouli Oil, Pepper, Black Oil, Pepper, Pink Oil, Peppermint Oil, Peppermint, Chocolate Oil, Peru Balsam Oil, Petitgrain Oil, Pimento Berry / Leaf Oil, Pine , pinyon oil, pine, scotch oil, pink pepper oil, pla oil, lambiarina oil, ravensara oil, ravintsara oil, rock rose oil, rhododendron oil, Roman chamomile oil, rosalina oil, rose oil, rose absolute and rose CO2 extracted rosemary oil, rosewood oil, sage, clary oil, sage, common oil, sage, dalmatian oil, sage, Spanish oil, sage, white oil, sandalwood oil, salo oil, scotch pine oil,Siberian fir oil, silver fir oil, spearmint oil, spike lavender oil, spikenard oil, spruce, hemlock oil, spruce, black oil, star anise oil, sweet myrrh oil, sweet orange oil, taget oil, tangerine oil, tansy, blue oil, Taiwan cypress (Taiwan cedar) oil, tea tree oil, common oil, tea tree, lemon oil, tea tree, New Zealand oil, thyme oil, tobacco absolute, tuberose absolute, tulsi oil, valerian oil, vanilla absolute and vanilla The extract may be an essential oil such as verbena, lemon oil, vetiver oil, violet leaf absolute, Virginian cedarwood oil, white camphor oil, white fir oil, white sage oil, wintergreen oil, xanthoxyllum oil, yarrow oil, ylang-ylang oil, yuzu oil, ethanol, butanol, lactic acid, ethyl acetate, gamma-valerolactone, silane (dihydrolevoglucosenone), epsilon-caprolactam, ethyl lactate, stearic acid, candelilla, carnauba wax No. 1 yellow, or beeswax. Other essential oils or precursors or monomers of other biological origin may also be used, if desired.

[0260] Preferably, the bio-based oil has double bonds or is easily volatile to evaporate and / or vaporize. Vaporized, aerosolized, and vaporized chemicals, including bio-based oils, are introduced into the plasma region generated by plasma module 20 and then polymerized. However, if the system is adapted to have oil applied by a pigment applicator, the oil preferably has double bonds in its structure to enable polymerization.

[0261] In at least one embodiment, organic and / or inorganic coatings can be applied. Inorganic coating precursors include pure metals, metal salts, oxides, nitrides, carbides, or combinations thereof. In yet another embodiment, the system 10 can coat a variety of particles ranging in size from nanometers to microns. The coatings can be deposited by precursors in either gas, liquid, or solid states, but preferably in vaporized or aerosol states.

[0262] Additionally, pigments having a size range of about 10 nm to about 100 nm can be used as components of larger molecular structures, typically in the range of about 100 nm to 1,000 nm. For example, pigments can be surface coated to increase their size, embedded in an acceptable carrier, or entangled or added to other particles or materials to create larger particles. In certain embodiments where at least one dimension of at least one pigment in a pigment solution is less than 50 nm to 100 nm, the surface of the pigment can be coated with a non-conductive matrix 10 nm to 100 nm or more thick to increase the size or particle size to 50 nm to 100 nm or greater. This size increase can increase the pigment supply for deposition onto Article 1.

[0263] In yet another embodiment, the pigment has optical absorption qualities between about 10 nm and about 10,000 nm, e.g., between 100 nm and 500 nm. Optionally, the pigment has optical absorption useful for excitation by standard laser devices or other light sources. For example, the pigment can be adapted to absorb wavelengths in the range of about 755 nm, between about 800 nm and about 810 nm, or between about 1,000 nm and about 1,100 nm. Similarly, the pigment can be adapted to absorb intense pulsed light in the range of about 500 nm to 1,200 nm.

[0264] The pigments provided herein can generally comprise aggregates of disaggregated pigments. By "disaggregated" pigments, we mean that the pigments in the aggregates are not linked to one another by physical forces or chemical bonds, either directly (particle-compound) or indirectly via an intermediary (e.g., particle-cell-moiety, moiety-protein-moiety, moiety-analyte-moiety). In other embodiments, the pigment compositions are assembled into an ordered matrix. In particular, the ordered matrix can comprise any three-dimensional matrix. In some embodiments, only a portion of the pigments are assembled, e.g., 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 86, 90, 95, 99%, or greater than 99% of the pigments are assembled in an ordered array. The pigments are assembled by van der Waals forces, London forces, hydrogen bonding, dipole-dipole interactions, covalent bonds, or a combination thereof.

[0265] The microparticles and pigments have an average diameter of about 10 nm to 10 μm and are distributed on the polymer surface at intervals of 10 nm to 3000 nm, and are structured depending on the size of the particles applied.

[0266] The plasma polymerized coating formed on the article by module 20 may be a protective coating that can be used to retard the diffusion of ions from the pigment therein, or it may be a functional layer that provides at least one functionalization selected from the group consisting of flame retardancy, UV absorption, self-cleaning, hydrophobicity, hydrophilicity, and / or antimicrobial properties. Other functionalizations may also be applied as known in the art.

[0267] Pigment or plasma polymerized coatings can be used to impart at least one of hydrophobic and hydrophilic functionality. Siloxane chemistry can be used to form hydrophobic and / or hydrophilic coatings on article 1. The functionality of such coatings can depend on the thickness of the coating, the porosity of the article being treated, and the pigment, if any, applied.

[0268] Hydrophilic pigments generally can include transition metals or their oxides or complexes. The pigments described herein can be included in plasma polymerized coatings and are typically applied simultaneously with the plasma coating or as part of an in-line process.

[0269] Some examples of hydrophobic pigments include manganese oxide polystyrene (MnO2 / PS), zinc oxide polystyrene (ZnO / PS) nanocomposites, precipitated calcium carbonate, carbon nanotube structures, silica nanocoatings, siloxane particles, etc. Fluorinated silanes, fluoropolymer coatings, and siloxane coatings can be used as binders for pigments while also providing hydrophobic functionality.

[0270] The hydrophilic pigment may be carried in a solvent during application, including ketones such as acetone or methyl ethyl ketone, alkanols such as ethanol or ethylene glycol, ethers such as diethyl ether, esters such as ethyl acetate, and acetonitrile. The solvent may be used to form part of the plasma-polymerized coating on the article after exposure to the plasma, or may be evaporated or substantially removed from the article before the plasma-polymerized coating is applied to the article.

[0271] Hydrophobic or superhydrophobic properties can be provided by plasma polymerized coatings alone, pigments alone, or a combination of both. Similarly, hydrophilic coatings can be provided in a similar manner.

[0272] A soft hand can also be imparted by the use of pigments and / or plasma-polymerized coatings. Soft hand is generally indicative of a textile or garment, where the hand of a treated substrate or textile generally remains unchanged or becomes even softer compared to the hand of an untreated substrate or textile. A softer hand can also be related to the drapeability of the substrate or textile. A key advantage of using plasma polymerization to produce a plasma-polymerized coating on a substrate is that it not only improves hand feel but also allows for functionalization. This is particularly true for plasma coatings that are applied by passing chemicals, monomers, or precursors through the plasma region generated by module 20 before being applied to the substrate.

[0273] Alternatively, a thinner coating can be applied by mist, vaporizer, or atomizer before being exposed to the plasma field for polymerization, however, this application method presents challenges as the applied fluid may agglomerate or solidify, resulting in an uneven coating under less than optimal conditions or if too much time is allowed between application and plasma treatment.

[0274] Plasma-polymerized coatings are preferably applied to articles during the plasma exposure step or by passing the chemicals, monomers, or precursors through the plasma zone before application to the article. This allows for greater control of coating thickness than traditional coating application methods such as dipping, knife coating, or spraying. The chemicals, monomers, or precursors that enter the plasma zone, preferably in droplet, vapor, or aerosolized form, can be readily fractionated and polymerized on the substrate to form highly crosslinked structures that can then be deposited on the article, allowing the coating or film to build or grow in the desired manner. Creating coatings or films in this manner can reduce the overall consumption of materials required to produce the desired functional coating on the article.

[0275] When self-cleaning or odor-resistant CuO, TiO2, and / or AgNO3 pigments are applied to article 1, ions from the copper or silver diffuse to the surface of the plasma-polymerized coating in which the pigments are embedded, creating a hostile environment for bacteria, microorganisms, viruses, or other biological agents. Alternatively, the self-cleaning coating may be the primary coating applied to article 1 to provide a self-cleaning coating. When exposed to sunlight, these coatings react with water to generate hydroxyl radicals. These radicals can decompose organic molecules and microorganisms adsorbed to the surface of the coating. When a fluid, such as water, is applied to the coating, it is absorbed and can remove or significantly remove dust, dirt, oil, and other contaminants from the surface. It is understood that other self-cleaning coatings are applicable and may have different activation or cleaning reactions, but any self-cleaning coating can be applied by system 10.

[0276] Self-cleaning coatings can be applied to clothing, medical devices, high-touch items, vehicles, airplanes, and public facilities. Multiple coatings can be applied or reapplied to the article 1 to achieve the desired properties of removing dirt, stains, oil, or other pre-determined contaminants.

[0277] Photocatalytic self-cleaning fabrics have used various semiconducting materials, including titanium dioxide (TiO2), zinc oxide (ZnO), and silica (SiO2). TiO2 has three different crystalline forms: anatase, rutile, and brookite. TiO2 can be used as a photocatalytic hydrophilic pigment, with the rutile and anatase phases being the main components.

[0278] Some pigments applied to articles can be useful in anti-friction coatings. Solid lubricants can be dispersed in articles to function as anti-friction coatings. Lubricating pigments can also be useful for improving the corrosion resistance or flame retardancy of articles. Anti-friction coatings form a slippery film that covers all surface roughness, optimizing metal-to-metal, metal-to-plastic, or plastic-to-plastic friction, even under extreme loads and operating conditions. Examples of anti-friction pigments in coatings can include materials selected from a non-exhaustive list that includes molybdenum sulfide (MoS), molybdenum disulfide (MoS2), PTFE, graphite, and specialty pigments. Additionally, pigments and coatings can be applied to improve the colorfastness or hand feel of the article after treatment.

[0279] UV-absorbing or photoprotective pigments can include mycosporine-like amino acids (MAAs). MAAs can be used to block or absorb UV-A and UV-B rays and absorb UV rays in the 310-360 nm range. Melanin pigments can also be used for UV protection. Furthermore, carotenoids and photopigments can be used as photoprotective pigments because they scavenge oxygen free radicals. Carotenoids and photopigments can also be used to supplement photosynthetic pigments that absorb light energy in the blue range.

[0280] In another embodiment, a pigment used in the process of forming a coating or film on an article can comprise at least one metal oxide from the group consisting of a metal oxide, such as SiO2, ZrO2, TiO2, Ta2O5, HfO2, ThO2, SnO2, VO2, In2O3, CeO2, CuO, CuS, FeCl2, ZnO, Nb2O5, VO5, Al2O3, Sc2O3, Ce2O3, NiO, MgO, YO3, WO3, BaTiO3, Fe2O3, Fe3O4, Sr2O3, TiO3, Cr2O3, Mn2O3, Mn3O4, Cr3O4, MnO2, RuO2, or a combination of these oxides, for example by doping or mixing the particles.

[0281] For coatings requiring biocompatibility, the coating can be adapted for use in in vitro applications and can optionally be a biopolymer as described herein, where the monomer or precursor for the plasma can include at least one of collagen, fibrin, fibrinogen, platelet-rich plasma, alginate, gelatin, albumin, and hyaluronic acid.

[0282] Other materials that can be injected or fed into the plasma region include the terpene β-elemene. Additionally, cyclic monomers suitable for ring-opening polymerization (ROP) can also be used. Optionally, these monomers may also be suitable for ring-opening copolymerization (ROCOP). Such suitable materials can include at least one or more materials selected from the group consisting of epoxides, cyclic trisiloxanes, cycloalkenes, lactones, lactides, cyclic carbonates, and amino acid N-carboxyanhydrides.

[0283] It will be appreciated that anionic ring-opening polymerization (AROP) and cationic ring-opening polymerization (CROP) can be achieved using plasma polymerization techniques. Additionally, ring-opening metathesis polymerization (ROMP) is also possible using plasma polymerization techniques.

[0284] In yet another embodiment, the system can be adapted to pre- or post-treat the article. Pre- or post-treatment is any form of treatment that the article may undergo to improve the interaction between at least one of the pigment and the plasma coating applied to the article 1. Pre- or post-treatment can be provided external to the system, but can also be used to improve the plasma coating and the pigment therein, if desired. For example, a heat treatment process can be used to remove moisture from the article before treatment, or a heat treatment can aid in curing the plasma coating after treatment. Other treatments, such as a cleaning process, a scouring process, ozone exposure, electrostatic cleaning, applying an electrical charge to the article, exposing the article to preset radiation and / or light, or plasma treatment, can also be provided. Such treatments applied to the article can improve the durability of the coating, the functional performance of the coating and / or the pigment within the coating, the hardness of the coating, the texture of the coating, the thickness of the coating, the color of the coating or the underlying article, the appearance of the coating, and the gloss of the coating.

[0285] The system can also provide single-sided and double-sided coatings. For example, a single-sided coating on a substrate article can be applied from a series of treatment modules positioned to face one side of the article. This is illustrated in FIG. 1, where all treatments on the treated substrate article face the first side. If there is a treatment module positioned to face the second side of the substrate article, the second side of the article can be treated during the same process. Alternatively, the first-side treatment module can be adapted to treat both the first and second sides of the article 1 by urging, forcing, or propagating the coating from the first side of the article to the second side of the article.

[0286] In yet another embodiment, the system can be adapted to pass an article through the system to process a first side of the article, and then re-feed the article through the system with the modules facing a second side of the article during re-feeding. This can include rotating the article before re-feeding, or repositioning one or more modules in the system to allow for processing of the second side.

[0287] System 1 allows an article to be coated with multiple treatments or single-sided treatments, thereby imparting one or more different functionalities to the article. For example, a substrate with a hydrophobic treatment on one side can be coated with a hydrophilic coating on the second side of the substrate. This is believed to be particularly advantageous when the substrate is porous, as the hydrophilic treatment is used to wick and transport moisture, while the hydrophobic treatment is used to transport and repel moisture in a desired manner. This can enable a moisture wicking system that does not require the use of multiple membranes, adhesive processes, or complex structures to achieve the desired wicking effect. Additionally, applying a hydrophobic treatment on the first side of a substrate article, a relatively hydrophilic treatment on top of the hydrophobic treatment, and a further hydrophilic and / or hydrophilic treatment on the second side of the substrate article, so that an intermediate layer of the coating thereon is suitable for moisture transport, can achieve other benefits.

[0288] Throughout this specification, the term "treatment" may be optionally substituted with the term "plasma polymerized coating." Throughout this specification, the term "pigment coating" may refer to a coating that includes a pigment formed from a plasma polymerized coating. Throughout this specification, the term "precursor, chemical, or monomer" may be substituted in certain embodiments such that the term is open-ended, unless it is desired to exclude one or more types of monomer, chemical, or precursor.

[0289] While specific examples of pigments have been described, pigments for each of the applications described above may also be suitable for one or more other functional applications, and thus any pigment described herein may be used in other embodiments disclosed herein, as appropriate. The size of the pigment may optionally be nanoscale or microscale, and / or include mixtures thereof.

[0290] Although the present invention has been described with reference to particular embodiments, it will be understood by those skilled in the art that the present invention can be embodied in many other forms consistent with the broad principles and spirit of the invention as described herein.

[0291] The present invention and the preferred embodiments described specifically include at least one feature that is industrially applicable. [Explanation of symbols]

[0292] 1 article 10 Systems 11 Terminals 12 frames 15. (15A-15C) Chamber 18 Pigment Applicator 20 modules 21 Post-processing module 22 Housing 30 power supply 40 Liquid Delivery Systems 45 Cooling System 50 Mixing Chamber 55 Sprayer 60 Laura 70 Recirculation System 80 Support 85 Pump System 90 Extraction System 95 Reservoir 100 electrodes 102 cores 104 Sheath 106 channels 108 fluid channels 110 Reaction Gap 112 Plasma Region 114 Gas Pipe 116 Aperture 118 Bias power supply 120 Bias 130 Carrier fluid supply unit 140 Monomer Supply Section 150 Pigment supply unit

Claims

1. 1. A system for coating an article, comprising: a pigment applicator adapted to apply the pigment; a plasma module adapted to generate a plasma region; and at least one of a chemical and a precursor supplied to the generated plasma, wherein the plasma region is capable of at least partially polymerizing the at least one of the chemical and the precursor to form a plasma polymerized coating; The system, wherein the pigment is fixed to the article by the plasma polymerized coating.

2. 10. The system of claim 1, The system further comprising a plasma post-treatment module adapted to treat the plasma polymerized coating.

3. 3. The system according to claim 1 or 2, The system, wherein the pigment applicator is integrated with the plasma module.

4. In the system according to any one of claims 1 to 3, The system, wherein the plasma module is housed in a chamber and is locally purged with a plasma gas to greater than 90% purity.

5. 5. The system of claim 4, The system is characterized in that an entrance to the chamber is fitted with a roller that seals the entrance, substantially retaining the plasma gas within the chamber and restricting the ingress of external fluids while allowing articles to enter the chamber.

6. In the system according to any one of claims 1 to 5, A system, wherein the pigment applied to the article is at least one of a colorant, a functional pigment, and a conductive pigment.

7. The system according to any one of claims 1 to 6, the plasma module is adapted to supply at least one of the chemical and precursor to the plasma region, the at least one of the chemical and precursor forming plasma polymerized molecules before being applied to an article to form a plasma polymerized coating.

8. A plasma coated article, a surface having a pigment deposited thereon; the pigment is attached to the article by a plasma polymerized coating; A plasma-coated article, wherein the plasma-polymerized coating is polymerized at a pressure of 95 kPa to 105 kPa.

9. 9. The plasma coated article of claim 8, A plasma coated article characterized in that a further pigment is deposited on the surface of the plasma polymerized coating.

10. 10. The plasma coated article of claim 9, A plasma coated article, wherein the further pigment deposit is secured to the plasma polymerized coating by a further plasma polymerized coating.

11. The article according to any one of claims 8 to 10, The article, wherein the pigment is provided to the article during a plasma polymerization step, and the pigment becomes bound within the plasma polymerized coating upon application.

12. The article according to any one of claims 8 to 11, The article is characterized in that the pigment has a size relatively larger than the thickness of the coating.

13. The article according to any one of claims 8 to 12, An article characterized in that the pigment is a colorant of a different color than the color of the article, thereby imparting to the article a hue or a color generally similar to that of the pigment colorant.

14. The article according to any one of claims 8 to 13, 10. An article, wherein the pigment is a functional pigment adapted to release and / or diffuse ions while bound within the plasma polymerized coating.

15. The article according to any one of claims 8 to 14, An article wherein said plasma polymerized coating is finished with a plasma post-treatment step to cure or otherwise treat exposed surfaces of said plasma polymerized coating.

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