Plasma coating film with particles

Abstract

A coating for application to an article containing a pigment or dispersion, the coating having an upper side and a lower side, the coating being applied to at least one surface of the article, the coating being formed from monomers and nanoparticles that have been passed through a plasma to form a plasma-polymerized coating.

Description

[Technical Field]

[0001] The present invention relates to methods and articles for coating. More particularly, the present invention relates to methods for producing particle-containing coating films and particle-containing articles, where the coating films are formed, at least in part, by a plasma polymerization process. [Background technology]

[0002] The development of superhydrophobic fabrics has been achieved by coating the surface of the fabric with a material that minimizes the surface free energy. The theory behind this is that morphology is modified to maintain low surface tension.

[0003] Many methods for achieving superhydrophobic surfaces on textiles rely on chemical solution treatments, which require chemical surface modification with oxidizing agents, such as chromic acid, and liquid reagents to generate reactive functional groups.

[0004] However, considering the number of potential methods for producing superhydrophobic coatings, there is a need to provide methods that can reduce the chemical processing required to effectively provide superhydrophobic coatings, as well as to provide methods that are less energy intensive.

[0005] While particles can be useful in a wide range of applications, the ability to provide these particles in coating films is generally expensive, results in undesirable thickness, a rough texture, an undesirable tactile finish, and generally does not provide a durable coating film, ultimately resulting in a less than desirable coating film.

[0006] Other functionalized or nanoparticle-containing coatings are also desirable. Nanoparticles can be organic or inorganic, and the addition of nanoparticles or other compounds can impart many properties to the coating.

[0007] It should be noted that the description of prior art in this specification does not imply an acknowledgment that the prior art is widely known or forms part of the general knowledge of those skilled in the art. Summary of the Invention

[0008] Problems that the invention aims to solve

[0009] It can be advantageous to provide the substrate with a virus-inhibiting coating.

[0010] It can be advantageous to provide a substrate with a nanoparticle coating that can be applied by plasma deposition.

[0011] It can be advantageous to provide a substrate with oligodynamic properties.

[0012] It can be advantageous to provide a coating that can be used to provide multiple functionalities.

[0013] It can be advantageous to provide a coating that can fix particles in a desired location relative to an article or substrate.

[0014] It would be advantageous to provide a coating method that can fix particles in a desired arrangement relative to a substrate or article.

[0015] It may be advantageous to provide a coating that can improve particle fixation and / or embedding.

[0016] It can be advantageous to provide a functional coating with a desired surface roughness.

[0017] It may be advantageous to provide a coating whose functionality can be changed by exposure to light.

[0018] It may be advantageous to provide the coating with one or more nanoparticles.

[0019] It would be advantageous to provide a method for simultaneously coating an article with nanoparticles and a protective coating.

[0020] 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.

[0021] In a first aspect, a coating film for an article can be provided. The coating film has an upper side and a lower side. The coating film can be applied to at least one surface of the article and can be formed from monomers and nanoparticles that have been passed through a plasma. Optionally, the nanoparticles can be of a microparticle size if they can be carried by a carrier fluid or the monomer.

[0022] Preferably, the monomer may be at least partially polymerized when introduced into the plasma. Preferably, the nanoparticles and monomer may be a dispersion or sol-gel solution that is atomized before being introduced into the plasma. Preferably, the monomer and nanoparticles pass through the plasma before being deposited on the article. Preferably, one or more nanoparticles may be present in the coating film. Preferably, the upper side of the coating film may be exposed to the atmosphere. Preferably, the upper side of the coating film may be configured to contact one or more pathogens. Preferably, the nanoparticles may have at least one of pathogen-inhibiting properties and oxidant properties.

[0023] In yet another aspect, a method for treating an article with a pathogen-inhibiting layer may be provided. The method may include positioning the article relative to a treatment module. A local atmosphere may be purged between the article and the treatment module. A plasma fluid may be supplied to an electrode region of the treatment module, the electrode region including two or more electrodes. A plasma gas may be ignited to form a plasma at the electrode region, and at least one of a monomer and nanoparticles may be supplied to the plasma at the electrode region, the monomer being polymerized by the plasma, and the nanoparticles being fixed to the article by polymerization of the monomer, forming a coating film on the article.

[0024] Preferably, the nanoparticles may be employed to release ions to disrupt the persistence of pathogens in contact with the coating film. Preferably, the nanoparticles may be distributed throughout the thickness of the coating film. Preferably, the processing module may identify the article beneath the electrodes and activate the electrodes corresponding to the size of the article. Preferably, the nanoparticles may be carried to the article by a carrier fluid. Preferably, the carrier fluid may be an aerosol, vapor, liquid, or gas. Preferably, a gas orifice may be employed to eject the monomer and nanoparticles into the plasma region and onto the article.

[0025] In the present invention, the words "comprise", "comprising" and similar words are to be construed in an inclusive rather than an exclusive sense, i.e., "including but not limited to".

[0026] The present invention is interpreted with reference to at least one technical problem described or associated with the background art. The present specification aims to solve or ameliorate at least one technical problem, 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]

[0027] [Figure 1] FIG. 1 shows an isometric view of an embodiment of a system for processing articles. [Figure 2] FIG. 2 shows a side view of an embodiment of a system including a roll-to-roll apparatus. [Figure 3] FIG. 3 shows a schematic diagram of an embodiment of a system for processing articles. [Figure 4] Figure 4A shows a side view of an embodiment of a treatment module that can be used to provide a coating to an article, and Figure 4B shows a side view of an embodiment of a treatment module that illustrates some of the plasma regions or effects that can be created. [Figure 5] Figure 5A shows a cross-sectional view of an embodiment of an electrode sheath of an electrode, Figure 5B shows a cross-sectional view of another embodiment of an electrode sheath of an electrode, and Figure 5C shows a cross-sectional view of a further embodiment of an electrode sheath of an electrode. [Figure 6] FIG. 6 shows a side view of an article having a coating film comprising nanoparticles applied thereto. [Figure 7] FIG. 7 shows a side view of an article having a coating comprising nanoparticles and a second coating applied thereto. [Figure 8] FIG. 8 shows a side view of an article with alternating treatments with nanoparticles in selected sections. [Figure 9] FIG. 9 shows a side view of the treated article with nanoparticles and an optional coating. [Figure 10] FIG. 10 shows a schematic of the experimental setup used to validate some embodiments. [Figure 11] FIG. 11 shows the K / S values of the color change of the experimental samples. [Figure 12] Figure 12A shows an example of a possible HMDSO fragmentation. Figure 12B shows an example of a possible HMDSO fragmentation. DETAILED DESCRIPTION OF THE INVENTION

[0028] Preferred embodiments of the present invention will now be described with reference to the accompanying drawings and non-limiting examples. [Explanation of symbols]

[0029] 1 article 10 Systems 11 Terminals 12 frames 15 chambers 20 modules 22 Case 30 power supply 40 Fluid Delivery System 45 Cooling System 50 Mixing Chamber 55 Sprayer 60 Roller 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 Tube 116 Opening 118 Bias Supply Source 120 Bias 130 Carrier fluid supply source 140 Monomer Source 150 Nanoparticle Sources 200 Base material 202 Top surface of the base 204 Bottom surface of base material 210 First Coating Film 212 Upper surface of first coating film 214 Underside of first coating film 216 particles 220 Second Coating Film 222 Top surface of second coating film 224 Underside of second coating film 226 particles

[0030] Described herein is a system for processing and fabricating materials, including substrates, sheets of material, 3D objects, and irregular objects, collectively referred to as "article" 1. While any desired article 1 can be processed with system 10, some embodiments refer to substrates or other planar articles. As such, the system is not limited to use solely in processing substrates 1.

[0031] FIG. 1 illustrates an isometric embodiment of a system 10 in which an article 1 is being treated and / or processed. The illustrated system 10 includes multiple treatment modules 20 used to treat a substrate 1. The treatment modules 20 may be showerhead modules, spray modules, deposition modules, plasma modules, or other treatment modules that can be used to activate or apply a coating to a surface. Each module 20 is removably attached to the system 10 and can be used to pre-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 nanoparticles and / or microparticles passing through a plasma from a head and being deposited onto the article 1.

[0032] The article 1 may be transported beneath the processing head 20 by a transport means. Any desired transport means may be used, such as a conveyor, a moving platform, rollers, or other predetermined means. Figure 2 shows one embodiment of the system 10, which uses rollers to transport the substrate article 1 into the chamber 15.

[0033] In another embodiment, multiple articles 1 can be placed beneath the treatment module 20 and treated without transporting the articles 1 from a first location to a second treatment location. This is particularly useful when coating or treating a single article 1 rather than a continuous group of articles on a production line. In this manner, the system 10 may function as a sterilizer, surface activation device, or selective treatment system.

[0034] The treatment module 20 may enable at least one of a physical change, a chemical change, a coating, application of a film, surface activation, sterilization, polymerization, or other desired treatment process, and the system 10 may include any number of modules for performing said treatments.

[0035] In a preferred embodiment, system 10 is configured to apply a pathogen-inhibiting treatment to article 1. The pathogen-inhibiting treatment may include a coating or treatment that reduces the persistence of pathogens on article 1, preferably killing, destroying, disrupting, or inhibiting the growth or life of pathogens on contact. The pathogen-inhibiting treatment may be an antiviral coating or antipathogen treatment configured to kill, disrupt, or inhibit specific viruses, bacteria, or microorganisms.

[0036] Antiviral and antipathogenic treatments are well known in the medical field and have a wide range of applications. These treatments can be any treatment, functionalization, or coating that provides a generally toxic or harmful surface that can reduce the persistence of pathogens. At least one of the nanoparticles and / or coatings applied to the article can provide a pathogen-inhibiting treatment.

[0037] Pathogens according to the present disclosure may include viruses, microorganisms, microbial agents, or bacteria. Viruses that may be inhibited by the present disclosure may include at least one of the following groups: influenza, measles, SARS-CoV, SARS-CoV-2, MERS-CoV, coronavirus, mumps, Marburg, Ebola, rubella, rhinovirus, poliovirus, hepatitis A, smallpox, chickenpox, severe acute respiratory syndrome virus or SARS virus (also known as SARS coronavirus), human immunodeficiency virus (HIV), and associated non-human animal immunodeficiency retroviruses such as simian immunodeficiency virus (SIV), rotavirus, Norwalk virus, and adenovirus. Norwalk virus includes its surrogate virus, feline calicivirus. Influenza viruses include human and avian viruses. Additionally, bacteria associated with hospital-acquired infections may be crushed, inhibited, or otherwise destroyed, including at least one of the bacteria causing the following infections: ventilator-associated pneumonia, methicillin-resistant Staphylococcus aureus, Candida albicans, Acinetobacter baumannii, Clostridium difficile, tuberculosis, urinary tract infections, vancomycin-resistant enterococci, and Legionnaires' disease.

[0038] The pathogen-inhibiting treatment or coating can be applied by a plasma polymerization or plasma treatment method. In one embodiment, the pathogen-inhibiting treatment passes through a plasma region and is then deposited on the surface. This is quite different from conventional plasma treatment systems, in which the plasma is used only to activate the surface of the article for conventional treatment application or to polymerize an existing coating on the article. This method has many distinct advantages over the prior art.

[0039] It will be appreciated that conventional plasma processing equipment also typically requires a vacuum chamber or chamber in which the article to be processed is placed. Because of numerous challenges associated with using plasma in a non-vacuum chamber, plasma is typically not used outside of a sealed chamber under reduced pressure. One such challenge is the even or uniform distribution of the carrier fluid and the monomers contained therein. Another challenge is that fluids introduced into the plasma region or reaction gap can cause polymerization of dangerous or unwanted molecules or ionization of molecules that could damage the substrate 1 during processing or affect the quality of the process. Therefore, the system module 20 described herein can be used to address these challenges.

[0040] In addition to the above, another significant problem with existing systems is that they are required to operate at a vacuum level. Not only does it take a significant amount of time to achieve a vacuum, but injecting an aerosol typically increases the overall pressure within the vacuum chamber, potentially leading to system malfunction. Aerosols injected into a vacuum tend to dissipate, rendering them unusable. Therefore, the systems and methods of the present disclosure offer significant advantages over known prior art.

[0041] It will be appreciated that in some embodiments, chamber 15 may have a pressure above atmospheric pressure when using gas delivery tubes or pressurized plasma fluids. This pressure may range from 10 Pascals to 1 MPa. In some embodiments, the pressure may be within a range of 5 Pascals to 100 Pascals. In certain embodiments, the chamber may be under pressure on the order of 50 Pascals ±20. Unlike conventional systems, the pressure increases and does not decrease toward a vacuum pressure. Therefore, system 10 may be configured to function at atmospheric or above atmospheric pressure.

[0042] Another important advantage of the system 10 is that it allows for the spraying of monomers and / or nanoparticles into the plasma region during the coating process. Spraying can be used to deliver nanoparticles, salts, organic particles, or inorganic particles to the plasma region or another desired location within the chamber 15. As previously mentioned, a sprayer can be used to convert at least one fluid into a vapor or aerosol. This vapor can be considered a form of "mist" and can contain one or more monomers and / or one or more nanoparticles. Optionally, small particles can be dispersed within the mist formed by the sprayer.

[0043] The aerosol is delivered to the chamber 15 via the fluid outlet and then introduced into the plasma region, either directly or by gravity. The aerosol may be directed toward the plasma region so that at least 50% passes through the plasma region and is then deposited onto the target area of the article 1. Using this method, coatings between 50 nm / min and 400 nm / min can be achieved. In some embodiments, coatings between 100 nm and 300 nm can be achieved. In yet another embodiment, the coating deposition rate is in the range of 150 nm / min.

[0044] In contrast, systems that utilize vacuum pressure cannot achieve coating because the pressure becomes too high when the aerosol is introduced into a vacuum or near-vacuum state. Furthermore, the aerosol quickly diffuses throughout the vacuum chamber before reaching the target area or plasma region 112. Even if a plasma region 112 could be created at the aerosol outlet, numerous plasma irregularities would occur when the aerosol was ejected. In this case, the polymerized plasma aerosol or activated particles would be dispersed within the chamber and would not flow in the desired direction. Conventional systems that utilize vacuum pressure or lower pressures also have other known drawbacks.

[0045] In yet another embodiment, nanoparticles can be entrained in an aerosol. In this manner, powders or particles of a desired size can be transported through a fluid system into the plasma region 112. In another embodiment, a separate stream of nanoparticles or clusters can be provided and mixed with the fluid exiting the outlet into the plasma region. Optionally, the nanoparticles can be sprayed, knife coated, wiped, or ejected onto the article 1.

[0046] In the embodiment of FIG. 1, the system 10 also includes a frame 12 to which a chamber 15 is mounted. Within the chamber 15, the article 1 can be treated with a plasma treatment process to inhibit pathogens or to provide a nanoparticle coating. The chamber 15 is preferably sealable and may form a fluid-tight seal to maintain a desired local atmosphere. The chamber may optionally have an inlet and an outlet to allow the planar article 1 to enter the chamber 15 for treatment and be removed from the chamber after treatment. The inlet and outlet 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, as seen in the embodiment of FIG. 2. The monomer source 140 and / or the sol-gel and / or dispersion source may be in fluid communication with the mixing chamber 50 so that the carrier fluid 130 can mix with the monomer from the monomer source 140 or the sol-gel from the respective supply. The carrier fluid may be, for example, an aerosol, vapor, liquid, or gas. There may be multiple monomer or dispersion sources, allowing for selective introduction of fluids from these sources. Fluid from the mixing chamber is fed into a circulation line (which may be a recirculation line if a recirculation system 70 is used), which then feeds the fluid into chamber 15. The carrier fluid is preferably a plasma gas that can be excited to form a plasma. For example, the carrier fluid may be an argon feed or another noble gas, which can be used to carry the monomer and / or dispersion to electrode 100 of processing module 20. Powering electrode 100 supplies electricity to the plasma gas, forming a plasma that can be used to polymerize the monomer and / or excite / activate the nanoparticles.

[0047] A terminal 11 is provided in communication with the system 10 and can be used to input variables, select fluids, monitor chambers, and start and stop processes. Any desired terminal interface may be used, and the terminal allows for movement of one or more components of the system 10. Software can be executed via the terminal and can be remotely updated. Storage media within the terminal 11 can desirably be used to store process data and to store data related to errors or unauthorized use or access within the system.

[0048] As seen in the schematic embodiment of Figure 3, an extraction booth or extraction system 90 may be provided to remove hazardous fluids from the chamber 15, ventilate the chamber 15, or remove volatile materials or atmospheric air from the chamber. The extraction system 90 may be used to exhaust the ambient atmosphere within the chamber and to inject or supply a controlled atmosphere into the chamber 15. A pumping system 85 may also be associated with the extraction system 90 or directly with the chamber 15 and may be used to evacuate the local atmosphere within the chamber 15 as needed.

[0049] The power supply 30 may be a generator or other mains power supply capable of supplying power to the system and its components. For example, the power supply may be connected to the process 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 process module 20, the electrode 100, and the bias plate 120. The article may be supported on a support 80, below which the bias 120 may be disposed. The bias may be a DC 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 promote the flow of polymerized monomers and / or nanoparticles toward and deposition on the article 1.

[0050] 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 can be a dielectric barrier discharge. The space between the electrodes 100, sometimes referred to as a reaction gap, is where a reaction between a voltage and a plasma fluid is observed, or where polymerization or fractionation of a monomer or polymer occurs. The monomer fraction may be located within a plasma region 112 located above, below, or between the electrodes, as illustrated in FIG. 4B. The plasma region 112 forms within the reaction gap 110 and may fill the entire reaction gap 110 or a portion of it. The space between the electrodes 100 may range from 1 mm to 12 mm, depending on the desired plasma density, and may be the reaction gap 110. The space 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. If the spacing is sheath-to-sheath spacing, the core-to-core spacing is greater.

[0051] Dielectric barrier discharges are typically characterized by the presence of at least one dielectric barrier, e.g., a sheath 104, and a reactive gap 110 located between each pair of electrodes 100. Dielectric barrier discharges may 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 sometimes referred to as "non-thermal systems," "non-equilibrium systems," or "low-temperature plasma systems."

[0052] 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 ions and uncharged particles (heavy particles) at a lower temperature than the electrons. Because the temperature of heavy particles in the plasma remains relatively low, dielectric barrier discharge burners have been described as suitable for polymerization and deposition processes, excluding undesirable polymer decomposition. The inherent advantages of dielectric barrier discharge systems over other conventional thermal plasma systems are that non-thermal plasma conditions can be easily established at or near atmospheric pressure and that they may also be used for the processing or polymerization of monomers and / or polymers.

[0053] System 10 can be used to deposit a variety of polymer coatings, polymer films, nanoparticle coatings, and nanoparticle treatments onto article 1. Non-limiting examples of coating monomers include at least one monomer selected from the following group: acetylene, ethylene, isoprene, hexamethyldisiloxane (HMDSO), tetraethoxysilane (TEOS), tetraethoxysilane, diethyldimethylsiloxane, 1,3-butadiene, styrene, methylstyrene, tetrafluoroethylene (TFE), methane, ethane, propane, butane, pentane, hexane, cyclohexane, acetylene, ethylene, propylene, benzene, Isoprene, hexamethyldisiloxane, tetraethoxysilane, diethyldimethylsiloxane, 1,3-butadiene m, styrene, methyl methacrylate, tetrafluoroethylene, pyrrole, cyclohexane, 1-hexene, allylamine, acetylacetone, ethylene oxide, glycidyl methacrylate, acetonitrile, tetrahydrofuran, ethyl acetate, acetic anhydride, aminopropyltrimethylsilane, ethoxyethane, ethoxyethoxyethanetriethoxyethanol, ethoxyethoxyethanetriethoxyethanol Triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane, triethoxyethanoethoxyethane Tricarbonyl(cyclooctatetraene)iron, dicarbonyl(methylcyclopentadienyl)iron, cyclopentadienyliron dicarbonyl (dimer), cobalt cyclopentadienylcobalt acetylacetonate, nickel acetylacetonate, dimethy(2,4-pentanedionate)gold(III), nickel carbonyl, iron carbonyl, tin acetylacetonate, indium acetylacetonate, indium tetramethylheptanedionate.

[0054] In at least one embodiment, organic and / or inorganic coatings may be applied. Inorganic coating precursors include pure metals, metal salts, oxides, nitrides, carbides, or combinations thereof. In yet another embodiment, the system 10 may be capable of coating a variety of particles ranging in size from nanometers to microns. The coatings are deposited by precursors, which may be in gas, liquid, or solid state.

[0055] Furthermore, nanoparticles having a size range of about 10 nm to about 100 nm can be used as building blocks for larger molecular structures, typically in the range of about 100 nm to 1,000 nm. For example, nanoparticles may be surface-coated to increase their size, embedded in an acceptable carrier, or entangled or added to other particles or materials to produce larger particles. In certain embodiments where at least one dimension of at least one nanoparticle in the nanoparticle solution is less than 50 nm to 100 nm, the surface of the nanoparticle may be coated with a non-conductive matrix 10 nm to 100 nm or thicker to increase the size or size to 50 nm to 100 nm or greater. This larger size allows for a greater supply of nanoparticles to be deposited onto the article 1.

[0056] In yet another embodiment, the nanoparticles have light absorption characteristics between about 10 nm and about 10,000 nm, e.g., between 100 nm and 500 nm. Optionally, the nanoparticles have light absorption characteristics useful for excitation by standard lasers or other light sources. For example, the nanoparticles may be adapted to absorb wavelengths around 755 nm, in the range of about 800 nm to 810 nm, or in the range of about 1,000 nm to 1,100 nm. Similarly, the nanoparticles may be adapted to absorb intense pulsed light in the range of about 500 nm to 1,200 nm.

[0057] The nanoparticles provided herein may generally comprise a collection of non-aggregated nanoparticles. "Non-aggregated" nanoparticles means that the nanoparticles in the collection are not linked to one another by physical forces or chemical bonds, either directly (particle-to-cell) or indirectly through an intermediary (e.g., particle-cell moiety, moiety-protein moiety, moiety-analyte moiety). In other embodiments, the nanoparticle composition is assembled into an ordered matrix. In particular, an ordered matrix can include any three-dimensional matrix. In some embodiments, only a portion of the nanoparticles are aggregated, e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 86%, 90%, 95%, 99%, or more than 99% of the nanoparticles are aggregated in an ordered array. The nanoparticles are aggregated by van der Waals forces, London forces, hydrogen bonding, dipole-dipole interactions, covalent bonds, or a combination thereof.

[0058] The microparticles and nanoparticles have an average diameter of about 10 nm to 10 μm, are distributed on the polymer surface at intervals of 10 nm to 3000 nm, and are structured depending on the size of the particles employed.

[0059] In one embodiment, the plasma impinging in the reaction gap 110 is formed at about room temperature and about atmospheric pressure. In at least one embodiment, the plasma generated in the plasma region 112 is preferably an atmospheric pressure plasma glow (APG). The APG may be enhanced by introducing a monomer into the plasma region or by the use of a Penning mixture. The monomer can be used as a low-ionization fluid that can form part of the plasma gas and Penning mixture. In some embodiments, the plasma gas is argon gas, and the monomer selected for polymerization has a low ionization threshold. Excitation of the carrier fluid may occur prior to injection of the monomer.

[0060] Preferably, a cold atmospheric pressure plasma (CAP) can be used to impart a desired pathogen-inhibiting or other functional coating to an article 1. CAP is a partially ionized gas (typical ionization rate of one ion or electron per billion neutral atoms or molecules) that interacts with the surrounding air to generate a reactive mixture consisting of electrons, ions, neutrons, excited atoms and molecules, reactive oxygen and nitrogen species, and ultraviolet light. Depending on the plasma source technology, carrier fluid, plasma operating parameters, and configurations such as transport mode and volume, the composition and concentration of the generated plasma species vary. This means that CAP can be "designed" to some extent, allowing different reactive species compositions to be generated by changing plasma input parameters such as carrier fluid, voltage, frequency, and other parameters that can be used to affect plasma density and / or formation.

[0061] The plasma may be generated by an electrical discharge between electrodes 100, which may excite or ionize a plasma gas to form said plasma. Any predetermined method may be used to generate the plasma, including alternating current (AC) excitation, direct current (DC) excitation, low frequency excitation, RF excitation, and microwave excitation. Atmospheric pressure plasma may be generated using any of the aforementioned methods. "Atmospheric pressure plasma," also known as atmospheric pressure plasma, is a plasma at a pressure approximately equal to atmospheric pressure. It will be understood that the pressure within chamber 15, even when filled with the desired local atmosphere, will be approximately the same as the pressure outside chamber 15. In at least one embodiment, the pressure within the chamber is approximately 1 bar to 5 bar, although other pressures above 1 bar may also be used.

[0062] Because plasma module 20 can be used in a local atmosphere, a carrier fluid for generating plasma in reaction gap 110 can be pumped into the region between article 1 and module 20 for a predetermined time such that the local atmosphere is evacuated from the region before igniting the carrier fluid to prevent ionization or activation of local atmosphere molecules. The region between article 1 and module 20 is sometimes referred to as the "local region." When system 10 is used in a sealed chamber, it may be desirable to purge the local atmosphere so that functional processing characteristics can be controlled. For example, purging chamber 15 can potentially remove oxygen within chamber 15 that could react with monomeric or polymerizing species and thus become free.

[0063] At least one additional fluid may be provided to the plasma region 112, either carried by the carrier fluid or injected directly into the plasma region 112. The additional fluid is typically used to treat the substrate 1 or apply a coating. In one embodiment, the additional fluid may be a monomer that can be polymerized by the plasma region and may 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 the carrier fluid and at least one additional fluid are supplied to the module 20, the fluids are preferably mixed in a desired ratio, and a known amount of the additional fluid is supplied to the substrate 1 through an outlet.

[0064] The monomer is injected into the plasma chamber 15 as a liquid spray, vapor, or particulates to aid in the formation of desirable plasma conditions, and the monomer may be employed to stabilize the plasma streamer or plasma corona conditions that form in the reaction gap 110. Stabilizing the plasma conditions may refer to forming a plasma glow or a stable plasma within the reaction gap 110. It will be appreciated that the voltage and frequency supplied to the electrode 100 also aid in maintaining and / or forming a stable plasma.

[0065] In yet another embodiment, when the article 1 is a substrate, the plasma may be used to treat only a first side of the substrate, while the second side of the substrate may be protected from treatment or may be treated separately with another coating or treatment process. This allows for selective modification of one side of the substrate. Protection of one side of the substrate may 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 have a coating or treatment applied to the second side.

[0066] The power supply 30 may include multiple power supply units. The power supplies 30 may be coupled to each module 20, allowing the modules 20 to be started, stopped, altered, or otherwise manipulated by a system user for the desired treatment process. 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 with a sheath 104 surrounding the core 102. 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. To reduce arcing and help stabilize the plasma formed in the reactive gap 110, the selected sheath 104 is formed from a dielectric material that can encase or encapsulate the core 102. Optionally, a fluid channel 108, such as an air gap or liquid gap, may be provided around the core 102, which may aid in the cooling and dielectric properties of the electrode 100. For example, air or an inert gas may be used as a cooling fluid passed between the electrode core 102 and the sheath 104. In another embodiment, the electrode 100 includes one or more fluid cooling channels or channels used to cool the electrode 100. Optionally, the core 102 may include fluid channels through which a fluid may be passed to cool the electrode 100. Examples of different electrode sheaths 104 are shown in Figures 5A-5C.

[0067] The electrode sheath 104 may be rectangular or circular, while the core 102 may be any predetermined shape that may or may not correspond to the shape of the electrode sheath. For example, the electrode 100 may be a blade-type electrode 100 with a rectangular sheath cross-section, while the core may be circular or another predetermined shape. The fluid conduit may have any predetermined cross-section, including a regular, sinusoidal, or wave-shaped cross-section. The general shape of the sheath 104 can define the type of electrode 100 regardless of the cross-section of the core 102, but it may be advantageous to match the shape of the core 102 to the shape of the sheath 104.

[0068] 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 different plasma treatment methods and exposure to plasma. In the local atmosphere, functionalization can impart groups including at least one of oxygen, nitrogen, and hydrogen groups. In another embodiment, plasma may be used to modify a surface by etching or removing material from the surface.

[0069] When the surface is activated, reactive groups may be present on the surface that can form good bonds with particles that interact with the surface. In another embodiment, the nanoparticles may be activated by plasma either directly by forming radicals from hydration water or by reaction at the surface of the nanoparticles.

[0070] The chamber 15 for subjecting the article 1 to plasma treatment is preferably purged with an argon or similar noble gas atmosphere at room temperature. Optionally, the temperatures of the argon, plasma gas, monomer, and solution are controlled to about 15°C to 50°C or higher, more preferably about 20°C to 35°C. The mixing chamber 50 or individual gas sources can also be heated or cooled. Heating the monomer, dispersion, or fluid polymer may increase the volume carried by the carrier fluid. For example, a substantial increase in the amount of hexamethyldisiloxane (HMDSO) monomer carried by the carrier fluid can be achieved by increasing the monomer temperature from 25°C to 50°C, resulting in a thicker coating film being applied in the same amount of time. It will be appreciated that each monomer used can have a different evaporation temperature or temperatures, allowing for a greater volume to be carried by the same volume of carrier fluid. However, it is desirable that the temperature of at least one of the monomer, carrier fluid, dispersion liquid, and mixing chamber be regulated or controlled to ensure that a desired volume and / or concentration of fluid is delivered to chamber 15 by delivery system 40.

[0071] In another embodiment, at least one consumable of the system, such as the carrier gas, monomer, dispersion, plasma gas, nanoparticles, or solution used in the system, is individually temperature-controlled. Each of these consumables can be temperature-controlled to a range of -10°C to +150°C. Other temperature ranges are possible, as long as they are between the freezing point temperature of the consumable and the vaporization temperature of the consumable upon introduction into the fluid supply line or plasma region. Increasing the temperature of some consumables can be advantageous, as it can increase the likelihood of fractionation upon entry into the plasma region and result in a more durable coating or a coating with desired properties. Furthermore, the carrier gas may carry at least one of the monomer, nanoparticle, or dispersion in greater quantities by increasing the temperature of the respective monomer, nanoparticle, or dispersion. Alternatively, the temperature of the carrier gas can be increased to further carry the monomer, nanoparticle, and / or dispersion.

[0072] Photoionization (PID) sensors, fluid flow sensors, temperature sensors, or other fluid sensors may be used within fluid delivery system 40 to monitor and control fluid distribution. The sensors may also determine the concentration and composition of the fluid extracted from chamber 15 for reuse in recirculation system 70. Based on the detected concentration and composition of the fluid extracted from chamber 15 and injected into recirculation system 70, the concentration and amount of virgin fluid from the fluid source can be varied to create a more uniform mixture. It will be appreciated that the recycled fluid and virgin fluid may collectively create the desired concentration delivered to chamber 15.

[0073] In another embodiment, the recirculation system includes a reservoir 95, which may be a tank or other container. Multiple reservoirs 95 may be provided that may be used to store separated fluids. For example, a first reservoir 95 may be used to store the carrier fluid and a second reservoir may be used to store the monomer or partially polymerized monomer. The reservoirs 95 may be used to temporarily store recovered fluids that may be reinjected into the recirculation system 70 or removed for further processing or purification.

[0074] The atomizer 55 may be used to atomize the monomers and nanoparticles that are carried through the fluid delivery system to the reaction gap 110. The atomizer 50 may be present in the mixing chamber 50. The mixing chamber 50 may be used to mix the nanoparticles and monomers in predetermined amounts to allow for a desired ratio of monomer to nanoparticles. A syringe or dosing means may be used to inject a predetermined volume of the monomer and / or nanoparticle fluid to be mixed in the mixing chamber 50, which may then be atomized. The mixing chamber forms part of the fluid delivery system 40.

[0075] Fluid delivery system 40 may also include a plurality of gas pipes 114, or conduits, to deliver fluid into chamber 15. Gas pipes 114 include a plurality of gas outlets 116 that allow pressurized gas to be distributed into chamber 15. Gas outlets 116 can supply pure substances, such as desired atmospheric gases, to chamber 15. Gas outlets can also allow at least one of a carrier fluid, a monomer, a monomer mixed with nanoparticles, nanoparticles mixed with monomer, and a dispersion to chamber 15. The dispersion preferably comprises polymerizable monomers and nanoparticles therein.

[0076] The gas outlet 116 can discharge the fluid in such a way that a flow is formed as the fluid passes through the plasma and toward the article 1. In this manner, a non-traditional type of plasma flow can be formed because the plasma gas can be released into the chamber atmosphere before being excited to form a plasma at the electrode 100. The plasma flow described above may be similar in appearance to plasma torches known in the art; however, it will be appreciated that, unlike plasma torches, the plasma flow forms above the excitation region, forming a cold stream of plasma. This is advantageous because the plasma flow is formed by the pressure of the fluid supply, passing through the free space above the electrodes before entering the plasma region 112. This provides the advantage that the carrier fluid can also enter the region above the electrodes, which can help smooth the plasma generated between the electrodes 100, or create a more uniform plasma that can extend across multiple sets of electrodes in the chamber 15.

[0077] The bias plate 120 may 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 and can attract particles from the module 20 down to the article 1. The bias plate 120 may be powered by the bias supply 118 or by the supply 30.

[0078] Preferably, bias plate 120 is a negatively charged DC bias plate. It will be understood that 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, if a Penning trap is used, the polarity of the Penning trap is opposite to the polarity of the bias plate, if present. A magnetic field may also be used to guide the movement of ions within the plasma region, urging positive and / or negative ions in a desired vector or direction.

[0079] 4A and 4B, an embodiment of a processing module 20 is illustrated. 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.

[0080] The outlets 116 may be located in a diffuser plate (not shown) to aid in the distribution of the carrier fluid and entrained particles or fluid. In the embodiment shown in FIGS. 4A and 4B , the gas conduits 114 are located with the 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 equal to or less than the number of reaction gaps 110, or may be two more than the number of reaction gaps. However, it will be understood that the number of gas conduits in a module may be any desired amount to allow sufficient delivery of fluid to the electrodes 100 and / or chamber 15.

[0081] Article 1 is shown relatively below module 20 and is configured to pass under module 20. By passing article 1 under module 20, a coating or treatment can be applied to article 1. Rollers 60 or supports 80 may be used to transport or convey the article from the first side to the second side of the module, with article 1' being the treated article. If the electrodes are energized to maintain a plasma within the reactive gap, a plasma region 112 can extend across multiple electrodes 100, as shown. It will be understood that the reactive gap is where the initial instance of plasma is formed, and the plasma region can ignite or excite the atmosphere local to the electrodes 100, causing the plasma glow. Preferably, the plasma glow is generally uniform across multiple pairs 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 does not need to directly interact with the article 1 unless desired. Fluids, such as carrier fluid, atomized monomer, monomer vapor, monomer aerosol, and / or nanoparticles, may enter the chamber 15 through the outlet 116. The fluid may disperse outward 124 through the holes, or sufficient pressure may be applied to form a fluid column 126. The dispersed fluid 124 can be used to spread the fluid across the electrode 100 and provide regions of different fluid densities, which can assist in the formation of a plasma region 112 that extends across multiple electrodes 100. Alternatively, the fluid column may be ignited to form a plasma stream. This plasma stream can be used in some embodiments to form spot coatings or more focused coatings. Unlike conventional plasma jets, the plasma stream is non-thermal, and the plasma fluid may be jetted into the open chamber 15 before reaching the electrode 100 to ignite or excite the plasma fluid. In this way, the fluid jetted into the chamber 15 can mix with the local fluid in the chamber 15 before reaching the electrode.This method of forming the plasma may also allow other gases within the chamber 15 that are not ejected from the outlet 114 to be entrapped or collected for transport to the reaction gap 110 .

[0082] Optionally, outlet 116 can be varied in size by the insertion of a nozzle or other flow direction or flow restriction device. Outlet 116 may be equipped with threads or mounting means capable of receiving a nozzle to vary the type or distribution of fluid flow entering chamber 15. Nozzles may also be used to direct the flow in a desired direction. Nozzles may be fitted with solenoids, irises, or closure devices, as needed, to seal the nozzle. This is particularly useful when multiple coatings or treatments are used within chamber 15, as the outlet can be selectively turned on or off.

[0083] 4B illustrates multiple circular electrodes 100, with a reaction gap 110 being the center-to-center distance between the circular electrodes 100, so that plasma can be formed between the electrodes 100 of opposing polarity. Other electrode cross sections can be utilized depending on the desired plasma to be formed, the desired coating film, or the desired cooling of the electrode or plasma temperature. A cooling system 45 may be used in conjunction with the electrode 100 to cool the sheath and / or core temperature to a desired temperature range, potentially helping to reduce damage to the article 1 being treated. The cooling system may be configured to communicate with the fluid channels 108 of the electrode 100.

[0084] A bias 120 may be provided below the article 1 and may be used to attract the article and / or fluid from the module 20 toward the article 1. The support 80 may be positioned relative to the article 1 and the bias 120, as seen in FIG. 4B . In another embodiment, the electrodes 100 may be collectively charged or coupled to a high voltage supply, and the bias 120 is grounded so that a plasma is formed between the electrode 100 and the bias 120. Forming the plasma between the electrode 100 and the bias 120 may allow the plasma to extend and engulf or more completely surround the article 1, compared to forming the plasma between a grounded high voltage electrode 100. It will be appreciated that in another embodiment, the bias 120 is charged with a high voltage supply, and the electrode 100 is grounded. 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 homogeneous and / or uniform plasma, which may promote more desirable coatings. The bias may be an electrical bias, such as a DC bias or a ground configuration.

[0085] A method for treating article 1 may include providing a polymer to a generally sheet-like or planar article, where the polymer is formed by plasma polymerization. Article 1 may have at least one fiber or thread exposed at a surface that can be treated by system 10. The polymer may 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 may depend on the density of the plasma, the coating time, and the volume of monomer introduced into the plasma region.

[0086] In another embodiment, the carrier fluid and atomized substance may be delivered to the chamber by the delivery system 40 and dispersed within the chamber via a diffuser plate (not shown). The diffuser plate may be positioned above the electrode 100 to ensure that the gas is more evenly dispersed across the electrode 100 at a generally uniform velocity. This may reduce spot coating that can be achieved by using pressurized gas from the gas outlet 116.

[0087] In yet another embodiment, module 20 may include a series of lasers capable of identifying the location of an article relatively below said module 20. Once the article is identified below module 20, electrodes directly above article 1 can be selectively turned on to form the desired plasma. In this manner, the entire module 20 does not need to be activated or energized, which is particularly valuable in that resources such as power, plasma gas, monomers, and nanoparticles can be conserved because they are not supplied to module 20 in areas where module 20 is not relatively above article 1.

[0088] In yet another embodiment, there is provided a method for depositing nanoparticles onto a substrate, comprising the steps of atomizing a colloidal solution (or suspension) containing nanoparticles, introducing the solution into a plasma region, and depositing the nanoparticles onto a surface of the substrate in the atmospheric pressure plasma.

[0089] Nanoparticles can be aggregates of small molecules or hundreds to thousands of atoms forming particles, with dimensions ranging from 1 nm to 100 nm. Larger particles can be carried by a carrier fluid, bound to a monomer, or transported with the aerosolized or evaporated monomer.

[0090] The dispersion can be used to apply the desired nanoparticles to the plasma-deposited coating. Any desired method of generating nanoparticles can be used with the process of the present disclosure. While nanoparticles are preferably used to form part of the coating film, larger particles such as microparticles can alternatively be used, provided they can be effectively transported to the coating area.

[0091] In yet another embodiment, the coating film can be formed from a dispersion coating film containing hydrolyzed monomers and / or nanoparticles. The dispersion can include, for example, a silicone-based compound such as tetrahydroxysilane (TEOS). Other dispersions can be used depending on the desired final functionality. In yet another embodiment, the dispersion can be used to apply pigments or nanoparticles to the article 1. The dispersion can be applied to the article 1 before it is exposed to the plasma from the module. Optionally, it may be desirable to remove, evaporate, dry, or extract the solvent from the dispersion from the article before it is subjected to plasma treatment or plasma coating. Solvent removal can be achieved using heaters, IR treatment, spectral wavelength exposure, exposure to ambient conditions, or evaporation techniques.

[0092] If the sol-gel coating exhibits brittle behavior, organic compounds or molecules can be incorporated. This can be achieved through the use of organically modified precursor compounds such as glycidoxypropyltrimethoxysilane (GLYMO), methacryloxypropyltrimethoxysilane (MEMO), propyltrimethoxysilane (PTMO), or any other desired precursor compound. Any precursor compound can be included as part of the sol-gel to improve the properties of the coating that may be applied to the article 1. The precursor may also impart at least one functional property to the coating that is applied to the article 1.

[0093] In a further embodiment, the system 10 is configured to transport inorganic and metal salts into the plasma region. When the salts interact with the plasma region, the salts may fractionate and elemental particles may be deposited on the article. For example, a copper salt may be introduced into the plasma region, and the salt may be ionized to cause separation of other elements from the copper salt. Preferably, the salt introduced into the plasma region comprises a reactive non-metal and a metal. Preferably, the reactive non-metal is a gas at room temperature, such as oxygen.

[0094] A solution or dispersion containing the salt can be injected or fed into a sprayer, which vaporizes the solution into an aerosol. Vaporization can be achieved by any conventional method, including thermal vaporization, ultrasonic vaporization, and evaporation. In some embodiments, sublimation can also be achieved by a sprayer. Because the monomer and fluid containing the nanoparticles may require relatively large droplets to allow effective particle transport, the droplet size can be controlled by the use of pressure and temperature of the monomer and / or nanoparticles. A plasma fluid can be used to transport the droplets into the plasma region 112. Preferably, the droplet size ranges from 0.1 nm to 500 μm.

[0095] The combination of the vapor and carrier fluid may form an aerosol, where the vaporized fluid is liquid droplets and the carrier fluid is a gas carrying the droplets. While aerosols can transport nanoparticles, it will be understood that some nanoparticles or pigments must be bound or dissolved in a solvent or solution before being converted to an aerosol. In some embodiments, nanoparticles or pigments in a dispersion may be sprayed onto the article 1 with a spray device rather than provided as an aerosol. Thus, when these aerosols enter the plasma region, the bound or dissolved nanoparticles are separated and converted back to their metallic or elemental state, which can then be deposited onto the article 1.

[0096] The sol-gel process is a method for forming inorganic materials dispersed in a solvent through the growth of metal-oxopolymers. The chemical reaction is based on inorganic polymerization. Metal alkoxides [M(OR)z, where M = Si, Sn, Ti, Zr, Al, Mo, V, W, Ce, etc., or alkoxy groups OC] are used. n H 2n+1

[0013] is used as a molecular precursor, and the metal oxopolymer is produced by hydrolysis and condensation reactions. Reactive hydroxy groups are first generated, followed by polycondensation.

[0097] In Class I organic-inorganic hybrid materials, the organic and inorganic components are bound together through weak bonds (van der Waals bonds, ionic bonds, hydrogen bonds, hydrophobic-hydrophobic balance), and these materials allow for a relatively large variety in the structures formed and the final properties imparted to the coating applied to the article 1.

[0098] For example, organic dyes can be embedded in a sol-gel matrix. As another example, organic molecules incorporated into an inorganic network can result in hybrid materials. Doping a sol-gel matrix with organic dyes, inorganic ions, or molecules can result in at least one property, such as fluorescence, photochromism, or nonlinear optical (NLO) properties, when the matrix is still in solution.

[0099] Organic molecules such as rhodamines, pyranines, coumarins, porphyrins, phthalocyanines, and spiropyrans can be encapsulated in inorganic networks such as silica, aluminosilicates, and transition metal oxide-based gels (ZrO2, TiO2). The selected inorganic matrix can be used to alter the refractive index and / or mechanical properties of the resulting coating. The inorganic molecular precursor (alkoxide), dye, and catalyst are mixed in a common solvent. The mixture is then hydrated to initiate polycondensation, resulting in the uniform entrapment of the dye molecules within the polymer. Weak interactions (e.g., hydrogen bonding, van der Waals forces) between the dye and the inorganic matrix explain the dispersion of the dye within the structure and contribute to the final properties of the coating, such as its photoresponsive properties.

[0100] Sol-gel inorganic matrices often have porous structures, typically with pores on the order of 1 nm. The pores of the structure can be filled with molecules by immersing the bulk in a solution containing a polymerizable organic monomer and a catalyst. Organic polymerization can be achieved by at least one of plasma polymerization, UV irradiation, a heating process, or a combination thereof. The system 10 can be adapted to treat the article 1 with at least one type of radiation using a suitable radiation-emitting device. Organic functional molecules can also be mixed with the organic monomer. Perylene dyes, as well as enzymes and porphyrins, can also be incorporated into these materials. These types of materials, including perylene dyes, enzymes, and / or porphyrins, may be advantageous for sensors and composite materials with longer-lasting luminescence properties.

[0101] The mechanical properties of polymer blends can be tailored by incorporating inorganic fillers within the monomer / polymer. The traditional process involves mixing the polymer (or prepolymer) with inorganic particles. This type of mixture has a high viscosity, which can lead to particle agglomeration. As a result, inhomogeneity within the material reduces the polymer-filler interaction. Optionally, a solvent can be used to alleviate homogeneity issues.

[0102] These techniques can also be used to produce ceramic fluids capable of forming shell-type ceramic coatings on articles. MgO, Al2O3, and SiO2 powders can be mixed with soluble polymers, and the viscosity of the gel can be adjusted by varying the concentration of the solute, which can aid in atomization. During polymerization, System 10 can more uniformly disperse particles from the sol, negating the drawbacks of non-homogeneous gels. Complex ceramics can be deposited by System 10 and then fired, calcined, or otherwise cured via plasma or by conventional firing methods.

[0103] The homogeneity of sol-gels can also be improved by embedding inorganic particles in the polymer. A typical method involves mixing a polymer and a metal alkoxide in a suitable solvent (alcohol or THF). A catalyst and water are then added to the mixture, allowing for in situ polycondensation. The highest homogeneity is achieved when the weak interactions between the two phases are sufficient to allow interpenetration of both networks at the molecular level. These materials have good optical properties, which can be varied by adjusting the silica:organic ratio.

[0104] Class II materials are hybrid structures in which organic and inorganic components are grafted together through strong covalent or ionocovalent chemical bonds. The molecules used as building blocks for Class II hybrids are alkoxy groups with at least two different functionalities (R-OM bonds), which should undergo hydrolytic condensation in the presence of water to form an oxopolymer backbone, and the metal-carbon bond is hydrolytically stable. The nature of the stable metal-carbon bond depends on the nature of the metal cation. Complexation with polyhydroxylated ligands, organic acids, hydroxy acids, p-diketones, and their derivatives is also used.

[0105] Colloids can include a mixture of particles in a fluid. The particles can be uniformly distributed throughout the fluid, which can be liquid or, in the case of a gel, solid. The particles can be soluble or insoluble within the fluid, and the particles can be organic, inorganic, or inorganic salts.

[0106] In one embodiment, a colloidal solution may be used, which may take various forms such as a liquid, a gel, or a slurry. Colloidal solutions are intermediate between a suspension, a heterogeneous medium of tiny particles dispersed in a liquid, and a true solution, in which one or more solutes are in a molecularly fragmented state in a solvent. In liquid form, colloidal solutions are sometimes called "sols." Colloidal sol-gel solutions are also sometimes called colloidal sols or soils.

[0107] When sol-gel synthesis is carried out in an organic medium from nanoparticle precursors, the preparation can include the following steps: step (a): hydrolysis-condensation of organometallic precursors or metal salts in an organic or hydroalcoholic medium; step (b): nucleation by maturation and growth of stabilized dispersed nanoparticles in an organic or hydroalcoholic medium; step (c): formation of an organic-inorganic hybrid sol, optionally by dispersion of the particles in an organic polymer or oligomer and / or by functionalization of the particle surface with any type of reactive organic functionality.

[0108] Sol-gel synthesis in organic media using different precursors (metalloid salts, metal salts, metal alkoxides) can be used to prepare sol-gels containing nanoparticles or pigments. Nanoparticles can thus be stabilized directly in the solvent used during synthesis or, if synthesized by precipitation, can be peptized later. Both methods result in suspensions.

[0109] Regardless of the preparation route chosen, the nanoparticle precursor can be selected from the group consisting of metalloid salts, metal salts, metal alkoxides, or mixtures thereof. For example, the metal or metalloid of the salt or alkoxide precursor of the nanoparticle can be selected from the group consisting of silicon, titanium, zirconium, hafnium, aluminum, tantalum, niobium, cerium, nickel, iron, zinc, chromium, magnesium, cobalt, vanadium, barium, strontium, tin, scandium, indium, lead, yttrium, tungsten, manganese, gold, silver, platinum, palladium, nickel, copper, cobalt, ruthenium, rhodium, europium, and other rare earths, or metal alkoxides of these metals.

[0110] As another example, an aqueous solution of metal salts can be reduced to colloidal metal nanoparticles. The reduction reaction can occur within the plasma region 112 upon excitation of the salt in solution. This can result in the formation of a polymer while simultaneously at least partially reducing the salt to elemental form. The elemental metal can then be embedded, bonded, or otherwise immobilized within the plasma-formed polymer. Unlike conventional plasma processing systems, nearly all of the monomers, or at least 60% of the monomers, fractionate upon passing through the plasma region, allowing the entire coating to form the desired crosslinks throughout the entire thickness of the polymer. More preferably, at least 80% of the monomers fractionate, at least 95% of the monomers fractionate, at least 97% of the monomers fractionate, at least 98% of the monomers fractionate, or at least 99% of the monomers fractionate. In contrast, conventional methods may activate or excite only the top layer of a pre-applied coating, resulting in only partial polymerization or partial crosslinking of the coating. As a result, such coatings may be weaker or less durable than those achievable with the system 10 of the present invention.

[0111] The fractionation rate is related to the overall efficiency of the system and may also be related to the plasma density and the volume of monomer injected into the chamber 15 to be polymerized.

[0112] In another embodiment, the sol can be prepared, for example, by synthesizing a solution of metal nanoparticles from precursors of the metal nanoparticles using an organic or inorganic reducing agent in the solution, for example, by a process selected from the group consisting of reduction of metal salts in an emulsion medium; and chemical reduction of organometallic or metal precursors or metal oxides.

[0113] Regardless of the process, the reducing agent may be at least one selected from the group consisting of polyols, hydrazine and its derivatives, quinone and its derivatives, hydrides, alkali metals, cysteine and its derivatives, and ascorbate and its derivatives. The precursors of the metal nanoparticles may be selected from any of the metal salts or metal or metalloid salts mentioned above.

[0114] In yet another embodiment, the sol can be prepared by preparing a mixture of nanoparticles dispersed in a solvent. However, regardless of the method by which the sol is obtained, more than one sol can be used, and more than one method can be used to derive each sol.

[0115] In another embodiment, the sol used in the process can be doped with or mixed with nanoparticles of a metal oxide, such as at least one oxide of SiO, ZrO, TiO, TaO, HfO, ThO, SnO, VO, InO, CeO, ZnO, NbO, VO, AlO, ScO, CeO, NiO, MgO, YO, WO, BaTiO, FeO, FeO, SrO, TiO, CrO, MnO, MnO, CrO, MnO, RuO, or a combination of these oxides. The above oxides are exemplary, and other metal oxides can also be used in the sol.

[0116] The size of the nanoparticles of the resulting sol is entirely controlled by the synthesis conditions, in particular the nature of the precursors, solvent, pH, temperature or other predetermined conditions. For example, for the applications mentioned herein, the nanoparticles preferably have a size between 1 nm and 100 nm, in particular to allow the production of thin layers or coatings with thicknesses in the range of, for example, 0.1 μm to 50 μm.

[0117] In addition to the nanoparticles, the sol also contains a carrier liquid, called the growth medium, that is generated during the manufacturing process. This carrier liquid can be an organic or inorganic solvent, as described in the aforementioned documents. For example, it can be a liquid selected from water, alcohols, ethers, ketones, aromatics, alkanes, halogens, and any mixtures thereof. The pH of this carrier liquid depends on the manufacturing process of the sol and its chemical nature.

[0118] In the resulting sol, the nanoparticles are dispersed and stabilized in their growth medium, although this stabilization and / or dispersion can be facilitated by the sol preparation process and the chemistry used. The sol can also contain organic molecules, which can be used to stabilize the nanoparticles in the sol and / or to aid in the functionalization of the nanoparticles.

[0119] Organic compounds can be added to nanoparticles to impart specific properties. For example, steric effects can stabilize these nanoparticles in liquid media, resulting in materials called Class I organic-inorganic hybrid materials. The interactions that govern the stabilization of these particles are weak hydrogen bonding and van der Waals electrostatic interactions.

[0120] Nanoparticles can be functionalized with organic compounds during synthesis by introducing appropriate organic-inorganic precursors or by grafting onto the colloidal surface. Examples are given above. These materials are called class II organic-inorganic materials because the interactions that exist between the organic component and the mineral particles are strong and covalent or ionocovalent.

[0121] The properties of hybrid materials depend not only on the chemical nature of the organic and inorganic components used to compose the sol, but also on any synergistic effects that may emerge between these two chemicals.

[0122] The temperature of the sol during injection can range, for example, from ambient temperature (20°C) to temperatures below the boiling point. Advantageously, the temperature during injection can be controlled and varied, for example, from 0°C to 60°C or any other desired temperature range. The sol has different surface tensions depending on the temperature, resulting in a more rapid and effective fragmentation mechanism when entering the plasma. Therefore, the temperature influences the quality of the resulting coating. This is particularly advantageous when using atmospheric pressure plasma, as the temperatures achievable are generally lower than those of thermal plasma jets.

[0123] The injected sol, for example in droplet form, enters the atmospheric pressure plasma region 112, where it breaks down into multiple droplets under the influence of the plasma's shear forces. The size of these droplets can be adjusted to impart the desired microstructure to the deposited coating and nanoparticle dispersion. Preferably, the average droplet size ranges from 0.1 μm to 10 μm. Furthermore, the microstructure can be varied by the type of plasma in the plasma region, its frequency, power, plasma density, and droplet temperature.

[0124] The atomizer is used to convert the sol into droplets and disperse the droplets in a carrier fluid. The velocity of the carrier fluid can direct the vaporized sol into the plasma region 112 where it is to be polymerized. The temperature of the plasma between the electrodes can be generally uniform so that fractionation occurs more uniformly throughout the plasma region 112. During fractionation, the nanoparticles can be adapted to agglomerate before being dispersed. The particles exiting the plasma region 112 are preferably uniformly dispersed on the following article 1.

[0125] The substrate to be coated is preferably positioned relative to the plasma jet so that the nanoparticle radiation is directed at the surface to be coated, for obvious reasons. It is very easy to find the optimum position through various tests. The positioning is adjusted for each application according to the selected projection conditions and the desired microstructure of the deposit.

[0126] The high deposition rate in the process of producing microstructured layers essentially depends on the mass fraction of the material in the liquid and the liquid flow rate. The method used with the system can provide deposition rates of nanoparticle coatings ranging from 0.01 μm / min to 100 μm / min. The deposition rate can be varied by changing the volume of monomer or sol-gel supplied, the electrode configuration, and the power supplied thereto.

[0127] A thin layer or coating film can be deposited on an article 1 with a thickness ranging from 0.1 μm to 250 μm (per minute of exposure). The nanoparticles in the coating film may be smaller in size than in the sol-gel, or on the order of a few nanometers to about 1 micron. The nanoparticles are optionally at least one of porous, dense, pure, and homogeneous. Preferably, the system allows for maintaining at least one of the properties of the starting sol in the coating and can be used to control at least one of the following properties: porosity, density, homogeneity, exotic stoichiometry (mixed sols and other mixtures), nanostructure (size and crystalline phase), particle size, and the possibility of deposition on any type of substrate, regardless of thickness, nature, and roughness of homogeneous deposits on objects with complex shapes.

[0128] This process can be repeated one or more times on the same article 1 or substrate 200 using different sol-gels or dispersions. The sols can have different compositions and / or concentrations and / or particle sizes, and successive layers of different coatings can be applied, or else compositional gradient deposits can be applied. Such successive layer depositions are useful in applications such as electrical layers (electrodes and electrolytes), optical layers (low and high refractive index), thermal layers (conductive and insulating), diffusion barrier layers, and / or layers with controlled porosity.

[0129] This spraying process can be applied industrially because its unique and innovative features lie in, among other things, the spraying system, which can be adapted to all thermal spray machines already existing in industry, the properties of the sol-gel solution, and the choice of plasma conditions to obtain nanostructured coatings with the properties of projected particles.

[0130] In yet another embodiment, a system 10 for coating a surface of a substrate 200 may be provided that includes a non-thermal plasma, a gas outlet capable of generating a plasma stream, a plasma gas reservoir, a nanoparticle sol reservoir, means for moving the substrate 200 relative to the plasma, and an atomizer for vaporizing the sol reservoir so that the sol vapor can be carried by a carrier fluid.

[0131] Advantageously, system 10 comprises a plurality of reservoirs each containing a plurality of sols loaded with nanoparticles, the sols differing from one another by their respective composition and / or diameter and / or concentration. System 10 may further comprise a cleaning reservoir containing a solution or solvent for cleaning, sterilizing or rinsing the fluid delivery system.

[0132] The flow rates and amounts of the carrier fluid and sol depend on at least one of the pressure in the mixing chamber, the pump used, the outlet 116, and the size of the aerosol droplets. The aerosol exits the gas tube via the outlet 116 at a pressure ranging from 1 bar to 5 bar. The internal pressure of the chamber 15 is preferably equilibrium. The outlet 116 may have any shape that allows the aerosol to be introduced into the chamber 15. For example, the outlet 116 may be a circle, a slit, a square, a rectangle, an oval, or another predetermined shape. Optionally, the wall thickness of the gas tube may allow for the formation of an angled exit conduit, a spiral conduit, or other predetermined structure that may impart fluid motion to the aerosol or aid in the dispersion of the aerosol within the chamber 15.

[0133] The orientation of the outlet 116 relative to the plane of the electrode 100 can vary from 20 degrees to 160 degrees, with 90 degrees being perpendicular to the plasma region 112. It will be appreciated that the plasma region 112 can extend to nearly the entire area between the electrode and the substrate 80 above the vias 120. The formation of the plasma region 112 is governed by the power supplied to the electrode 100 and / or vias 120, the spacing between adjacent electrodes, and the spacing from the electrode 100 to the vias 120. The outlet 116 may also be displaced relative to the plasma region 112. In this manner, the injection of vaporized or aerosolized sol and carrier fluid into the plasma region 112 can be directed. This orientation allows for optimization of the injection of the sol, and therefore the formation of a coating projected onto the surface of the substrate.

[0134] Preferably, the fluid reservoir is thermostatically controlled to control and modify the temperature of the sol as it enters the mixing chamber. This temperature control and temperature modification can be implemented to aid vaporization and to improve the surface tension of the sol, which may aid vaporization, aerosolization, and / or polymerization.

[0135] In yet another embodiment, a direct injection system can be used to deliver the aerosol to chamber 15. With this system 10, a stable suspension of nanoparticles can be injected directly into the chamber rather than being vaporized in a mixing chamber and carried to chamber 15 by a carrier gas.

[0136] System 10 may enable application of a coating to article 1 in which the size of the deposited nanoparticles is the same as the size of the sol, the particle distribution is uniform in the coating, the state of homogeneity is preserved, and the porosity of the deposited coating is controlled. The system is preferably adapted to deposit 70% or more by weight of the vaporized fluid within chamber 15. The system also provides for a relatively low temperature coating to be applied to article 1, which is advantageous for both heat-sensitive sols and article 1 that cannot be exposed to relatively high temperatures or prolonged periods of high temperatures. The relatively high temperature may be 100°C or higher.

[0137] The coating from the system 10 can be applied and deposited well onto an article 1 having a surface roughness while maintaining a mechanically resistant and adherent coating.

[0138] The system 10 can be useful in one or more technical fields where it is necessary to obtain a nanostructured coating. The system 10 can be used to provide a relatively homogeneous coating with respect to nanoparticle dispersion, coating thickness, and particle size (especially with respect to agglomerated particles). The metal and / or oxide coating can be used to make the article 1 corrosion resistant.

[0139] Deposition of wear-resistant composite coatings. Deposition of coatings that can withstand high temperatures, such as the deposition of high-temperature resistant materials and composite coatings. Deposition of coatings that participate in the interaction of surfaces in relative motion (tribology), such as wear-resistant composite coatings and lubricants.

[0140] Deposition of coatings involved in energy conversion and storage, such as coatings involved in photothermal conversion of solar energy. For these types of coatings, the colloidal sol coatings can be in the form of stacks of active materials for electrodes and electrolytes in solid oxide fuel cells, electrochemical generators such as lead-acid batteries, lithium-ion batteries, and supercapacitors.

[0141] In another embodiment, the atmospheric plasma is a low-temperature atmospheric plasma. The low-temperature dispersion plasma may be a partially or fully ionized gas having a temperature ranging from -20°C to 180°C. The pigment or nanoparticle dispersion may be fed directly to the plasma region 112 or may be fed to the article 1 before being processed by module 20.

[0142] The nanoparticles that can be used to form part of the coating film can be nanoparticles of a metal, a metal oxide, a metal alloy, or a mixture thereof. Optionally, the nanoparticles are nanoparticles of at least one transition metal, its corresponding oxide, an alloy of a transition metal, or a mixture thereof.

[0143] The nanoparticles can be selected from the group formed by silver, aluminum, magnesium, strontium, titanium, zirconium, chromium, tungsten, iron, cobalt, nickel, platinum, copper, gold, zinc, tin, lead, their oxides, or other predetermined metals or alloys. Other suitable nanoparticles can include at least one of the group consisting of titanium dioxide, copper oxide, zirconium dioxide, and aluminum oxide. In yet another embodiment, a system selected from the group formed by gold / platinum (AuPt), platinum / ruthenium (PtRu), cadmium / sulfur (CdS), and lead / sulfur (PbS) alloys can be used.

[0144] Some nanoparticles are oligodynamic in nature and can be produced from precursors selected from the group consisting of triphenyltin hydroxide, triphenyltin acetate, thallium sulfate, silver sulfadiazine, silver nitrate, thiomethyltriphenyllead, copper sulfate, barium polysulfide, and other precursors or nanoparticles described above. It will be understood that nanoparticles produced or used to come into contact with human skin or tissue are desirably non-toxic and desirably non-nephrotoxic.

[0145] The plasma fluid for forming the plasma is selected from the group consisting of argon, helium, nitrogen, hydrogen, oxygen, carbon dioxide, air, or mixtures thereof. It will be appreciated that the plasma gas is preferably a noble gas and does not interact with the chemistry of the monomers or nanoparticles injected or fed into the plasma region.

[0146] A method for depositing nanoparticles according to at least one embodiment of the present invention includes passing a nanoparticle-containing dispersion or a nanoparticle-containing suspension through a plasma region to deposit on the surface of the article 1. It will be appreciated that the nanoparticles may be pigments with sizes ranging from nanometers to micrometers.

[0147] This system offers many advantages, including eliminating the need for traditional wet coating processes, which are typically resource-intensive. Furthermore, depositing nanoparticles and / or plasma-polymerized monomers onto the substrate surface allows for greater control over the coating, reducing the likelihood of contaminants being incorporated into the coating. Furthermore, this system can also be used to coat low-surface-energy materials that are otherwise difficult or impossible to coat. For example, low surface energy can be associated with hydrophobic or near-hydrophobic materials, and it may be desirable to coat materials with even lower surface energy. Coating can be achieved by activating a low-surface-energy surface, which can be either a coating or a substrate surface. Furthermore, the ease of coating low-energy surfaces allows for the application of thinner coatings. This is because the coating does not need to seal or bond with other components to achieve a durable final coating. Therefore, system 10 allows for thinner coatings that can be limited to one side or do not need to encapsulate the substrate's threads or fibers. Furthermore, system 10 allows for the deposition of particles onto low-surface-energy surfaces, potentially providing better adhesion than traditional coating methods. This is particularly important with polyamides, which are generally liquid-repellent and are also commonly used in personal protective equipment such as gowns and masks.

[0148] As a result, the present system 10 can be used to provide thinner antibacterial or antipathogenic coatings that can be applied to surfaces that have previously been difficult or impossible to coat. Furthermore, the coating thickness can be in the nanometer range, rather than micrometers or greater. The system 10 may also coat only one side of a porous substrate without coating or protecting the second side, which is not possible with conventional processing methods. Such coating techniques are also useful for face masks, medical gowns, personal protective equipment, and other commonly disposable medical supplies.

[0149] Optionally, a surface activation step may be used in which article 1 is exposed to plasma, which can enhance the adhesion of subsequent particles, such as nanoparticles and polymer coatings, that come into contact with article 1. The preliminary plasma treatment can also control the surface properties of the interface between the coating (including nanoparticles) and article 1.

[0150] A colloidal solution of nanoparticles may be prepared by any predetermined method known in the art and then selectively injected into a mixing chamber where it can be mixed with the monomer and / or carrier fluid.

[0151] In yet another embodiment, clusters of nanoparticles can be deposited on the surface of Article 1, affixed to the surface of Article 1, or embedded in a polymer coating that is adhered or affixed to Article 1. The deposited nanoparticles may be organized into packets of nanoparticle clusters that generally have particle sizes similar to those of the initial colloidal suspension.

[0152] The nanoparticles or pigments may receive an electric charge when introduced into the plasma region, which may aid in cluster formation. The advantage of clusters is that the release sites of the article 1 may be more concentrated. A release site is a site from which a pathogen-inhibiting effect can be released or diffused. For example, the release site may diffuse or emit ions that may destroy cell walls or other pathogen structures. Conversely, the nanoparticles or pigments applied to the article 1 may be uncharged to minimize attractive forces, avoiding aggregation or clustering of the nanoparticles or pigments for more uniform distribution on the article 1.

[0153] System 10 may inject a sol-gel or dispersion comprising nanoparticles or pigments into the plasma region. The sol-gel or dispersion may be atomized or evaporated before being injected into the plasma region. If the sol-gel or dispersion is applied to article 1 before exposure to a treatment process from the module, it may be advantageous to remove all portions of the liquid sol-gel and / or dispersion, leaving only the nanoparticles or pigments on the article, allowing them to be fixed with a plasma coating.

[0154] In yet another embodiment, it may be desirable for the nanoparticles to be disrupted or otherwise reduced in structure or size as they pass through the plasma region, so that they can be dispersed throughout the coating film being applied to the article 1. It will also be understood that the general size of the nanoparticles does not change upon passing through the plasma. Using this method for applying nanoparticles may avoid the use of stabilizing additives, such as dispersants and surfactants, that are common in the art when applying nanoparticles.

[0155] Preferably, the coating applied to the article is homogeneous, with the nanoparticles evenly distributed across the treated surface. Optionally, system 10 may provide for the supply of nanoparticles to the fluid supplied to the plasma region such that certain areas of article 1 are coated with nanoparticles and other areas are not.

[0156] Preferably, the limited exposure to the plasma does not permanently change the properties of some of the nanoparticles, thereby allowing the nanoparticles to function or behave as expected within the coating film. Alternatively, the nanoparticles may be permanently altered by the exposure to the plasma and become "activated" after exposure. This may result in a chemical or physical reaction occurring on the surface of the article 1 or within the polymeric portion of the coating film. For example, some of the nanoparticles may be in a charged state and may form oxides or compounds with the coating film or the plasma fluid.

[0157] If the article 1 has been used prior to plasma treatment, the surface of the article 1 desired to be coated may optionally be cleaned to remove organic and / or inorganic contaminants that may prevent deposition or coating from being achieved on the surface. Additionally, cleaning the article may also improve adhesion of the coating film. Cleaning the article 1 may be performed by physical, chemical, radiation, or mechanical cleaning methods. In yet another embodiment, cleaning of the article occurs when the article 1 is subjected to plasma.

[0158] Within the sol-gel or dispersion, one or more types of nanoparticles can be provided, each nanoparticle adapted for a given function, for example, first nanoparticles can be biocidal nanoparticles and second nanoparticles can be reactive nanoparticles that react with the surface of the article 1.

[0159] In one example, the nanoparticles preferably have a size between 1 nm and 100 nm, in particular to allow the production of thin layers or coatings, for example with thicknesses in the range of 0.1 μm to 50 μm. In another example, the pigments described herein may have a size in the range of 1 nm to 250 microns.

[0160] The sol-gel can be mixed with a carrier fluid, which is a mixture of monomer and plasma gas. This mixture can then be injected into the plasma region or dispersed in the plasma region. To aid in transporting the monomer and / or sol-gel (or nanoparticles therein) into the plasma region, it is preferable to atomize the monomer and / or sol-gel. Furthermore, atomization also ensures that a larger portion of the mixture fed into the plasma region is successfully ionized within the plasma region, or otherwise provides more effective polymerization of the monomer.

[0161] Preferably, all fluids supplied to the article or system are temperature controlled so that fluctuations in external conditions do not affect the feed rate and respective concentrations of pigment, monomer, or nanoparticles.

[0162] The kinetic and thermal energy of the plasma is used to disperse the polymerized monomer and nanoparticles onto the article 1. A coating having a plurality of nanostructure deposits can be formed on the surface of the article 1, where the polymer coating polymerizes and embeds and / or encapsulates the uniformly dispersed nanoparticles within the coating. This method advantageously avoids traditional wet coating processes, which do not provide a consistent distribution of nanoparticles compared to the present invention. Furthermore, avoiding traditional coating methods provides greater certainty that a desired volume of nanoparticles will be fixed onto the article 1.

[0163] While the present method of applying nanoparticles to an article 1 has many advantages, the present method is particularly advantageous for articles that cannot be subjected to wet processing methods. For example, while textiles, fabrics, and other substrates can be successfully processed using traditional wet coating methods or the application methods disclosed herein, the application of coatings to electronic devices cannot be achieved using such traditional methods. Thus, the present method of applying nanoparticles to an article can be particularly advantageous for electronic devices.

[0164] In one embodiment, the monomer is a suspension or solvent for the nanoparticles, and the monomer and nanoparticles are collectively referred to as a "sol-gel." As discussed herein, other types of sol-gels may be used in system 10. Optionally, the sol-gel may comprise part of the final coating composition and may be mixed with one or more other sol-gels, vaporized fluids, or evaporated fluids to form the coating film.

[0165] The process of the present invention can be carried out several times on the same substrate surface using sol-gels with different compositions, concentrations and / or particle sizes. Applying one or more layers to the article 1 can be advantageously used to provide coatings that offer different functional properties or can help improve abrasion resistance if a lamination effect is desired.

[0166] In yet another embodiment, the system may employ applying a conductive coating, the coating comprising nanoparticles applied by a plasma treatment process.

[0167] The coating may be applied using a stencil or spot coating method. Spot coating is a focused coating method that can leave a "spot" or localized coating or deposit on the article 1. Spot coating methods can optionally utilize a stencil or other coating to more precisely apply the coating to the article 1. As the article 1 moves relative to the module 20, the stencil can inhibit or block portions of the article from being coated, leaving a stencil pattern on the article 1. This is particularly advantageous when depositing aesthetic coatings, such as photoluminescent, reflective, conductive, or other coatings that can be viewed under certain conditions. Optionally, a focal spot coating can be achieved such that the article 1 does not move relative to the module 20 during stencil application.

[0168] The first process provides nanoparticles that are covered with a non-conductive coating, which can then be used to form conductive coatings for clothing and other electronic textiles. Additionally, flexible films can also be formed using the methods described herein.

[0169] The electrodes 100 may be spaced apart at will. They may consist of parallel, grounded, hollow, circular or oval tubes of any desired diameter. It is preferred that the electrodes 100 be uniformly spaced to reduce the likelihood of corona discharge during use, which could damage the electrodes 100. The spacing may be the maximum distance that allows a desired plasma density to be formed. Additionally, the electrodes 100 preferably have a uniform diameter or cross-sectional area.

[0170] 5A-5C, several embodiments of electrodes that can be attached to a processing head are shown. FIG. 5A shows a circular electrode having a circular core. The core 102 of the electrode 100 is received within a channel 106 sized to correspond to the diameter of the core 102. This provides a relatively tight fit between the channel 106 and the core 102, and during use, the core 102 is held within the channel with minimal axial movement.

[0171] It will be appreciated that the core 102 and sheath 104 may be concentric, with the outer shape of the sheath 104 being sized to generally correspond to the shape of the core 102. In another embodiment, the core 106 is formed with fluid channels 108 through which a fluid can be passed to cool the electrode 100 during use. Fluids used to cool the core include, for example, water, inert gases, oxygen, nitrogen, and coolants. Fluids may also be used to impart motion to the generated plasma, which may be varied by increasing or decreasing the flow rate of the cooling fluid through the channels 106.

[0172] 5B shows a rectangular electrode sheath 104 with a rectangular core 102. The electrode 100 is a "blade" electrode because the length of the electrode exceeds the width of the electrode. Optionally, the electrode 100 may have one or more fluid channels 108 that allow the passage of a coolant. The coolant may include an inert gas, water, or other predetermined fluid.

[0173] FIG. 5C illustrates yet another embodiment of an electrode 100 that can be used in the present system. The electrode 100 includes multiple cooling channels 108. Each cooling channel 108 may be the same size as the core channels 106 formed for the electrode core 102. Optionally, each channel 106, 108 may be attached to a respective core 102 to which power can be supplied to excite the plasma gas. It will be appreciated that a pair of electrodes 100 is required to form a region in which plasma can form. Each channel is preferably uniformly spaced within the electrode sheath 104, with the outermost channels having a thickness to the outer surface that corresponds to the spacing between the channels. Other shapes and configurations may be used depending on the shape of the core 102 and the desired plasma to be formed.

[0174] The outer surface of the electrode is "stadium" shaped, or more simply, a rectangle with rounded ends. Having rounded ends reduces the possibility of monomer and / or particles accumulating on the electrode 100 and also reduces the possibility of harmful fluid flow from the system. Preferably, the electrode 100 is shaped to promote fluid flow toward the article 1 to be coated.

[0175] Referring to FIG. 6, a substrate 200 is shown having a first coating film 210, a pathogen-inhibiting layer, that provides antibacterial or pathogen-inhibiting properties. The first coating film 210 comprises a polymer having a dispersion of one or more nanoparticles selected from titanium, aluminum, zinc, gold, silver, cesium, copper, calcium sulfate, strontium, barium, zinc sulfide, copper sulfide, titanium dioxide and barium zeolites, brass, mica, talc, kaolin, mullite, or silica, their oxides, and any other inorganic or organic nanoparticles. Additionally, lead or mercury compounds may also be used depending on the application. The thickness of the first coating film 210 on the substrate may range from 5 nm to 200 nm, although thicker coatings can be applied as desired depending on the speed of the substrate and the deposition rate of the module 20. The nanoparticles may be substantially pure metals (95% or greater purity, more preferably 99% or greater purity), metal alloys, or sulfides or sulfates of the aforementioned metals.

[0176] The coating film 210 may be a polymer coating film formed by a plasma polymerization process and used to embed and fix nanoparticles in an article. The coating film 210 has an upper surface 212 that contacts the article 1 and a lower surface 214. The upper surface of the first coating film 210 may be in direct contact with the second coating film 220. Similarly, the second coating film 220 also has an upper surface 222 and a lower surface 224. The article 1 has an upper surface 202 and a lower surface 204, and the upper surface is coated with the first coating film 210. It will be understood that multiple surfaces of the article 1 may be coated with the first and / or second coating films.

[0177] The surface at which a coating film contacts, bonds to, or reacts with article 1 is referred to as an interface. Similarly, the surface between a first coating film and a second coating film may be referred to as an interface between the coating films. Since any number of coating films may be provided on article 1, each contacting coating film may have its own interface.

[0178] The polymer of the coating film may be a functional coating film or may simply be used to secure nanoparticles to the article 1. Optionally, the article 1 includes one or more nanoparticles thereon or therein before being plasma-treated. While the thickness of the first and second coating films is generally the same, the first and second coating films can each have any desired thickness. Furthermore, while the coating films 210 and 220 are generally shown as linear, the coating films may be etched, contoured, or textured in any desired manner. Optionally, the surface of one or more coating films may be textured using a mold, heat treatment, or further plasma treatment. Texturing the surface of a coating film can improve at least one of the adhesion, grip, feel, softness, surface retention, or other desired properties of an additional coating film to be applied.

[0179] Referring to FIG. 7, a further embodiment of article 1 is shown. The article is a substrate 200 including a first layer 210 having nanoparticles and a second layer 220 that is a functional coating layer. The ions of the nanoparticles in the first layer can be configured to release, migrate, or diffuse through the second layer to impart a pathogen-inhibiting effect to the surface of the second layer. The second layer 220 can be a protective coating that can be used to slow the diffusion of ions from the first layer 210, or it can 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 antibacterial properties. Other functionalizations can also be applied as known in the art.

[0180] Referring to FIG. 8, a substrate 200 is illustrated having a first coating with nanoparticles and a second coating without nanoparticles. The first coating 210 and second coating 220 can be applied using a stencil that covers a portion of the article 1, in this example, the substrate 200, to allow the desired coating to be applied. The stencil can then be removed and replaced with a second stencil that is a negative of the first stencil, allowing the second coating to fill any gaps or spaces between the first coating. In this manner, the first and second coatings can be applied substantially flush. Alternatively, a second stencil is not required, and the second coating 220 is applied over the first coating 210 and the substrate 200. This can induce undulations or surface texture on the top surface of the second coating. The nanoparticles 216 in the first coating 210 can be conductive nanoparticles or can form a conductive coating with the surrounding polymer, allowing for the passage of electrical current. Such coatings can be used for flexible circuits, electronic clothing, or other conductive purposes. Optionally, second coating 216 may include nanoparticles 226. This type of coating may be advantageous because article 1 may be treated with a variable coating that can selectively provide functionality.

[0181] FIG. 9 illustrates a further embodiment of the article 1, which is a substrate 200 having first and second coating films 210, 220. The first coating film 210 is applied directly to the substrate 200, and the second coating film 220 is applied on top of the first coating film. Each of the first and second coating films 210, 220 contains nanoparticles 216, 226, which may be the same or different nanoparticles. If the nanoparticles 216, 226 are the same, the polymers used to attach the nanoparticles to the surface of the article 1 may be different, each with their own functional properties. The formation of multiple coating films can be used to form a laminate that can act as a barrier for ion diffusion from the nanoparticles, or to divert, slow, or inhibit the rate at which ions or nanoparticles react or diffuse between coating films. The lower surface of the second layer may be chemically or mechanically bonded to the upper surface of the first coating film.

[0182] Optionally, a primer or intermediate layer can be provided between one or more layers to aid in bonding of the plasma-treated or plasma-formed coating. A primer can also be used to influence the chemical reaction on the top surface of the article 1 to achieve desired properties. For example, a primer can be used to improve the bond between the article and the first coating 1. In another example, the chemical reaction between the primer and the coating can increase or decrease the stiffness of the article bearing the coating. Other properties may be desired or achieved through the use of other primers or local atmospheric conditions within the chamber 15.

[0183] In yet another embodiment, the coating applied to article 1 can be etched to expose the numerous nanoparticles deposited on the substrate. In yet another embodiment, article 1 may be etched before receiving the coating or during the coating process. Etching can aid in the deposition of nanoparticles and provide recesses into which the nanoparticles or coating can be deposited at a relatively large thickness.

[0184] Other physical or chemical vapor deposition processes may be applied to the article 1 prior to treating the article 1 with the plasma system 10. In this manner, the article may receive multiple coatings, where the coatings are applied to, layered on, or otherwise deposited in discrete areas of the article 1.

[0185] In at least one embodiment, at least one coating preferably comprises pathogen-inhibiting nanoparticles so that the coating can be used to destroy, inhibit, kill, or inactivate pathogens that contact the surface of the coating.

[0186] In a preferred embodiment, the pathogen-inhibiting coating contains copper and / or silver as a pathogen-inhibiting substance. Silver and copper have been observed to be effective against bacteria, as silver and copper ions are used to denature proteins in target bacteria by binding with reactive groups. This binding causes pathogens to precipitate and become inactive. Silver has also been shown to inhibit enzymes and metabolic processes. Cationic species are electrostatically attracted to the negatively charged cell walls of bacteria. Cationic antimicrobial peptides have been shown to be effective in inhibiting the regulatory mechanisms of target bacteria.

[0187] Therefore, the present invention also provides a composition containing the nanoparticles described above for use as an anti-pathogen agent. The nanoparticles can be suitably formulated in a suitable carrier, coating agent, or solvent, such as water, methanol, ethanol, acetone, water-soluble polymer adhesives such as polyvinyl acetate (PVA), epoxy resins, and polyesters, coupling agents, or antistatic agents. Solutions of biological materials, such as phosphate-buffered saline (PBS) and simulated biological fluids (SBF), can also be used.

[0188] The application of the agent can be done by one of the following methods: spray coating, electrospray coating, dipping, plasma coating, plasma polymerization, etc. Other processes can also be used to achieve a suitable coating film.

[0189] Protective clothing articles can be prepared from suitable fibers and fabrics, including natural and synthetic fibers. Natural fibers include cotton, wool, cellulose (including paper materials), silk, wool, jute, hemp, sisal, flex, wood, and bamboo. Synthetic fibers include polyester, rayon, nylon, Kevlar®, lyocell (Tencel®), polyethylene, polypropylene, polyimide, polymethyl methacrylate, poly(carboxylatophenoxy)phosphazene PCPP, fiberglass (glass), ceramic, metal, and carbon. Clothing can be selected from the group consisting of face masks (surgical masks, respirators), hats, hoods, pants, shirts, gloves, skirts, boiler suits, and surgical gowns (scrubs). Such clothing can be particularly useful in hospitals, where infection control is critical.

[0190] According to another embodiment, there is provided a method for reducing and / or preventing viral infections, comprising applying to a filter a nanoparticle composition as defined above, wherein the application of the nanoparticle composition can be carried out via a plasma treatment or plasma polymerization process.

[0191] 6-9, an embodiment of article 1 is shown, designated substrate 200. Substrate 200 may be a film, textile, fabric, or any other desired generally planar surface. A pathogen-inhibiting layer may be applied to substrate 200 by system 10. The pathogen-inhibiting layer may be, for example, first coating 210 or second coating 220. While flat surfaces are preferably treated with the coating, coatings may also be applied to irregular or textured surfaces, or to three-dimensional objects such as electronic devices and their peripherals. Multiple coatings may be applied to the surface of the object or substrate 1 to achieve the desired functionality or pathogen-inhibiting treatment.

[0192] The textile or fabric may include at least one of nylon, polyamide, rayon, polyester, PP, PET, PE, aramid, acrylic, acrylate, paper, wool, silk, cotton, linen, Kevlar®, lyocell (Tencell®), fiberglass, glass, woven fabric, nonwoven fabric, knitted fabric, knitted fabric, insulation, synthetic materials and fibers, natural materials and fibers, organic materials, or other materials suitable for use in apparel, PPE, face masks, filters, drapes, bedding, wall coverings, and upholstered products. Textiles are understood to be substrates 200 (woven or knitted) formed of threads, filaments, strands, or fibers interconnected in a regular or orderly manner, or, in the case of nonwovens, bonded substrates 200. These textiles have pores or interstices between the fibers, threads, filaments, or strands, which makes them breathable, a highly desirable characteristic for apparel and many filtration devices and media.

[0193] Because the gaps and pores in the fibers can increase the overall surface area of the fiber's lateral surface, the pathogen-inhibiting layer applied thereto can also have a generally large surface area, which is advantageous for capturing or inhibiting pathogens. The pathogen-inhibiting layer can also be formed to increase the overall surface area or to have at least one texture to increase the surface area, for more effective pathogen inhibition. The pathogen-inhibiting layer can vary in thickness to enable different pathogen-inhibiting applications or pathogen-inhibiting durations. For example, a relatively thick pathogen-inhibiting layer can extend the pathogen-destruction duration compared to a thinner pathogen-inhibiting layer or compared to a conventional coating film containing dispersed nanoparticles.

[0194] While silver and copper have been shown to produce such modifying effects, other inorganic materials may also have many advantages that can be used for self-cleaning, self-sterilizing, biocidal, pathogen-inhibiting, pathogen-killing, and oligodynamic effects.

[0195] Other metals and inorganic materials that can be used may be selected from titanium, aluminum, zinc, gold, silver, cesium, copper, calcium sulfate, strontium, barium, zinc sulfide, copper sulfide, titanium dioxide and barium zeolites, mica, talc, kaolin, mullite, or silica. Additionally, lead or mercury compounds may also be used depending on the application. The average diameter of the deposited metal can range from 0.01 to 200 microns, preferably from 5 to 100 microns.

[0196] The fibers receiving 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.

[0197] The inorganic particles, or core material, may be any of the oxides of titanium, aluminum, zinc, copper, calcium, strontium, barium, or lead. As indicated, the material may also be a sulfide or sulfate. It is preferred to use near-pure metals or metal alloys to form the nanoparticles of the pathogen-disintegrating layer. However, it will be understood that other compounds, such as silver nitrate (AgNO3) or titanium dioxide (TiO2), may also be used.

[0198] The term "pathogen disruption layer" is used herein to describe a material deposited by a plasma or plasma polymerization process, which may include any of the inorganic materials described above, that is used to kill, destroy, inhibit, or otherwise destroy pathogens that come into contact with the deposition surface or ions released therefrom.

[0199] The pathogen-disrupting layer can be deposited on the substrate by chemical vapor deposition, physical vapor deposition, sol-gel deposition, or a combination thereof. The pathogen-disrupting layer can be a first coating, a second coating, and / or an additional coating applied to article 1.

[0200] Applying a pathogen-inhibiting layer to the substrate 200 can enhance the pathogen-inhibiting substrate. Furthermore, the combination of the pathogen-inhibiting layer fiber and the pathogen-retaining or soil / chemical-retaining filter media provides various functions, including but not limited to pathogen control, chemical control, and soil control, while maintaining low pressure drop and high water flow rate during use. This can be particularly useful in air filtration, water purification and filtration, and other fluid capture and cleaning applications. It may also be particularly useful in laboratory extraction systems and personal protective equipment, face masks, and garments. Furthermore, because the surface of the mask can be coated to generally sterilize or decontaminate it, previously single-use masks and gowns used in medical settings can be reused multiple times without any or significant degradation in filtration or safety. This is particularly advantageous for face masks for seasonal influenza, colds, COVID-19 strains, and other virus filtration devices.

[0201] The filter media can be any substrate capable of filtering, retaining, or capturing particles traveling in the same plane as the filter media. The filter media can be positively or negatively charged and can attract particles of the opposite charge. Additionally, the filter media can be a nonwoven material or a generally porous material that allows the desired fluid to pass through while capturing contaminants and other particulates. The pathogen-inhibiting layer can be applied directly to the filter media or can be combined with the filter media to form the article 1. It will be understood that in some embodiments, the article 1 can be a filter media with at least one coating, where the coating is a pathogen-inhibiting layer.

[0202] The combination of a pathogen inhibition layer and a filter media is considered desirable because it allows the filter media to capture and retain pathogens, allowing the pathogen inhibition layer to kill, destroy, inhibit, or destroy the captured pathogens for an effective period of time. Furthermore, in applications such as filtration masks, it is preferable to maximize the interstices between fibers and the pore size of the filter material to ensure the desired breathability. However, large interstices and pore sizes reduce the potential for physical capture of particulates, so electrically charged fibers may be used to attract and retain particulates to the filter media.

[0203] In another embodiment, a filter substrate or filter media may be provided. The filter media may be comprised of a silver- or copper-coated fabric that has been subjected to at least one functional treatment. It will be understood that any of the pathogen-inhibiting deposits mentioned herein may be applied to the filter media. Optionally, a membrane that can be used for soil filtration and / or capture, and / or a chemical-retaining membrane, and / or a pathogen-retaining membrane, or a combination thereof, may be included. The membrane may be disposed between the substrate and the coating, such as by applying the coating directly to the membrane. The membrane may be integrally formed with the substrate 200, or may be fixed or adhered to the substrate 200.

[0204] Furthermore, the present invention, at least in preferred embodiments, relates to the use of textiles coated with silver vapor deposition (or other biocidal materials) to form pathogen-retaining filter media, to provide filter media with enhanced pathogen killing, and in pathogen-destroying or pathogen-inhibiting protective equipment.

[0205] Thus, a preferred embodiment of the present invention provides a filter medium comprising a microbiocidal membrane. The microbiocidal membrane comprises a fabric having deposited thereon a film that destroys at least one pathogen or microorganism. The filter medium preferably does not contain an adhesive layer or adhesive paste that may cause blockage of the pores or gaps in the fabric or membrane.

[0206] When the substrate 200 is a nonwoven material, the nonwoven material may be a sheet structure of continuous filament polyester or polypropylene fibers, randomly aligned, highly dispersed, and bonded together at filament junctions. The chemical and thermal properties of spunbond polyester are essentially those of polyester fibers. The spunbond structure of this fiber combines physical properties such as high tensile and tear strength, smooth edges, excellent dimensional stability, no media migration, excellent chemical resistance, and controlled arrestance and permeability. Spunbond polyester or polypropylene fabrics are used in various industries as coverings (e.g., medical gowns and masks) and supports. They are also used in the medical industry and other personal protective equipment and disposable products.

[0207] Spunbond polyester or polypropylene fabrics contain straight or crimped polypropylene or polyester fibers, which give the fabric different filtration and other common performance characteristics. Crimped fibers are considered to be softer, more conformable, and have higher porosity, while straight fibers are considered to be stiffer, tighter, and have finer arrestance.

[0208] The pathogen-inhibiting layer of the present invention can provide a surface that reduces pathogen activity, thereby reducing the persistence of potentially dangerous pathogens on the surface. For example, the SARS-COV-2 virus has been shown to persist on certain surfaces for several days, but when exposed to treated textiles, its persistence is reduced to 5-60 minutes. Preferably, up to 99.9% of pathogens exposed to the surface are inactivated after 60 minutes.

[0209] Optionally, substrate 200, if comprised of fibers, may be formed with at least one antibacterial or antipathogenic chemical or nanoparticle within the fiber structure. For example, the fibers of substrate 200 may include ion-releasing silver or copper nanoparticles in addition to the pathogen-inhibiting layer.

[0210] In one embodiment, the nanoparticles 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 nanoparticles can be protected, covered, or have a functional coating applied after deposition to prevent the nanoparticles 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 applied as known in the art.

[0211] Reduction and / or prevention of viral transmission can be defined as a reduction of infectious viral titer of a known concentration of virus by at least 99.9% after exposure to treated textiles. Preferably, the reduction in infectious viral titer is at least 99.9%, 99.99%, or 99.999%. Reduction and / or prevention of viral infection is demonstrated by inactivation of the virus after exposure to treated textiles.

[0212] The nanoparticles 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, or polyesters, coupling agents, or antistatic agents. Solutions of biological materials, such as phosphate-buffered saline (PBS) or simulated biological fluid (SBF), can also be used. The concentration of the nanoparticles in the solution ranges from 0.001% (wt) to approximately 20% (wt). These nanoparticles can form a coating that can be applied to the substrate 10.

[0213] In yet another embodiment, article 1 may include multiple pathogen-inhibiting layers capable of releasing ions to inhibit pathogens. It may be advantageous to have multiple pathogen-inhibiting ions present on the surface to more effectively inhibit pathogens.

[0214] In a further step, article 1 may be treated by a physical vapor deposition (PVD) or chemical vapor deposition (CVD) process before being processed by system 10. Plasma-enhanced PVD or CVD processes may also be used if desired and may be referred to herein simply as "PVD" and "CVD." The material applied in a PVD or CVD process may be in the form of a film or may be a generally uniform coating.

[0215] Thus, a method of coating a PVD or CVD film is contemplated by the present disclosure, wherein the electrode 100 is displaced relative to the PVD / CVD coated article 1 during this process so that adverse plasma conditions are prevented or otherwise limited. For example, corona discharges and other plasmas that may damage the article 1 may form in the presence of conductive materials or surfaces.

[0216] The primary advantage of applying films using the above methods is that the overall thickness of the coating film is nanoscale to microscale, and the use of adhesives can be completely eliminated, as adhesives are a vapor characteristic of condensing on the substrate, providing bonding bonds. This also helps reduce the distance between layers in composites or multilayer structures, allowing electrostatically charged materials to be relatively effective when combined with at least one PVD / CVD film or coating and / or anti-pathogen coating. Another advantage is the ability to form relatively thin and flexible structures, as adhesives can degrade the overall properties of the resulting structure. Note that adhesion depends on the mechanical properties of the two materials brought into contact. However, using vapor deposition methods can provide at least a weak bond that can be encapsulated or protected by further coatings or treatments, such as those applicable by system 10. Adhesion is also affected by the relative contact angle of the vapor to the substrate, the temperature of the vapor, and the condensation rate.

[0217] The metal nanofilm morphology of the film applied to article 1 can also play a significant role in many properties, such as anti-pathogen properties, conductive properties, surface roughness, reflectivity, and aesthetic properties. In this way, system 10 can be used to apply coatings that protect films or coatings applied by PVD / CVD processes and help reduce the oxidation rate or chemical change of one or more other properties of the film. Plasma coatings from system 10 can also impart additional properties, such as hydrophobic coatings. A key advantage of applying thinner coatings from system 10 is that the emissivity properties of the applied film are negligibly affected by the addition of the protective coating, or generally have no observable effect on the film's emissivity. In this way, surfaces with excellent reflectivity and low emissivity can be created that are not achievable with current technology.

[0218] Furthermore, because PVD, CVD, and system coating methods can all be applied as single-sided coatings (i.e., without dipping or other encapsulation), the described methods may have the primary advantage of imparting desired properties to one surface of a substrate while leaving the second surface of the substrate substantially the same as it was prior to deposition or coating, a method not available to those skilled in the art, much less capable of coating at such relatively thin film thicknesses.

[0219] Optionally, multiple layers of films and plasma coatings can be applied in any desired configuration. Plasma coatings can also be applied prior to PVD or CVD processes to improve adhesion or to provide a protective coating on the substrate before depositing a metal film or coating. Optionally, a PVD or CVD coating can be sandwiched between two plasma coatings to provide a conductive layer for electronic textiles or other desired conductive materials.

[0220] Deposited films may also be etched by plasma coating or plasma treatment. Such etching can be applied with a plasma stream to localize the etching location, or with a stencil. Other etching techniques can also be used to selectively etch at least a portion of the metal film. The etched areas may be filled with organic or inorganic nanoparticles or pigments. Optionally, layers above and below the metal film can be used to etch the applied metal film.

[0221] In another embodiment, application of the pigment or nanoparticles to the article 1 can include an evaporation or other removal step to remove the solvent, gel, dispersion, or solution in which the nanoparticles or pigment were provided. After this removal step, the article 1 with the nanoparticles or pigment can be treated with a plasma treatment before being coated with a further step of plasma coating. It will be understood that plasma treatment can be used before application of the nanoparticles or pigment, after application of the nanoparticles or pigment, and after application of the plasma coating. Each of the plasma treatment steps can be adapted to aid in fixing the pigment or nanoparticles and can also be used to impart desired functionality or properties to at least one of the nanoparticles, pigment, or plasma coating.

[0222] Optionally, multiple coatings of the same material can be applied to the substrate 200, with a first coating applied to the top surface of the substrate and a second coating applied to the top surface 212 of the first coating 210. Alternatively, first and second coatings 210, 220 can be applied to the top and bottom surfaces of the substrate 200. It is clear that in these two extreme cases, continued deposition will result in films of the same material, but with significantly different nanoscale structures and morphologies, resulting in significantly different properties such as density and adhesive behavior. Optionally, a pathogen-inhibiting layer can be disposed below the self-cleaning layer to enable the surface of the article 1 to be self-cleaning (e.g., to remove oily stains) and also inhibit pathogens that come into contact with the surface of the article.

[0223] For example, a self-cleaning TiO2 or AgNO3 layer can be applied over a pathogen-inhibiting layer, such as a layer containing copper or silver ions. Ions from the silver or copper layer can diffuse to the top surface of the self-cleaning layer, promoting an environment hostile to bacteria, microorganisms, viruses, and other biological agents. Alternatively, the self-cleaning coating can be a primary coating applied to the article 1 to provide the self-cleaning coating. When exposed to sunlight, these coatings can react with water to generate hydroxyl radicals. These radicals can decompose organic molecules and microorganisms adsorbed to the coating surface. Application and absorption of a fluid, such as water, can remove or substantially 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 the system 10.

[0224] Self-cleaning coatings can be applied to clothing, medical devices, high-touch objects, vehicles, airplanes, public facilities, etc. Multiple coatings can be applied or reapplied to an article 1 to achieve the desired properties, such as removal of dirt, stains, oil, or other predetermined contaminants.

[0225] It will be appreciated that the use of magnetic nanoparticles or coatings to form pathogen-inhibiting layers may exhibit superparamagnetic properties when the particle size is less than about 20 nm. Thus, controlling the particle size distribution may have applications beyond or complementary to the pathogen-inhibiting properties. For example, the superparamagnetic properties may be particularly useful in the electronics field.

[0226] The article 1 of the present invention is also useful as an air or water filter media. These filters are used to purify fluids or capture unwanted contaminants in the fluid. The filter media is preferably formed from a substrate having at least one of a pathogen-retaining medium and a pathogen-inhibiting layer. Optionally, the pathogen-inhibiting layer in this embodiment may be a membrane or may be deposited / applied onto a membrane used in the filter media. Optionally, the membrane may be the article 1 comprising the substrate 200 and at least one coating film formed via a plasma polymerization process.

[0227] In another embodiment, Article 1 may be a protective barrier such as a gown, wall covering, drape, curtain, sheet, or another substrate used to form a barrier against the environment or a barrier to reduce or inhibit the penetration of fluids or particles in fluids, such as pathogens.

[0228] Pathogen retention media can be used to capture pathogens by providing a physical barrier or by providing an electrostatic charge that can attract and capture pathogens. This is because pathogens have an electrical charge and are attracted to electrostatically charged substrates. At least one pathogen retention media may be included within article 1, and a coating, which may be a pathogen-inhibiting layer, may also be included to enable article 1 to capture and inhibit or destroy pathogens. It is understood that the protective barrier and filter media may be comprised of the same substrate and coating. As such, the term "filter media" may also refer to the "protective barrier" herein. Pathogens that may be captured or captured by the pathogen retention media may be killed or inhibited by ions from nanoparticles in the coating or by the chemistry of the coating, if the chemistry is virucidal or biocidal.

[0229] The filter media may further include a soil or chemical retention filter media to capture larger particles before they interact with the pathogen-inhibiting layer to reduce potential biological fouling of the filter. As used herein, the term "biofouling" refers to the accumulation of microorganisms on the surface or pores of a pathogen-inhibiting layer or another coating associated with the filter media.

[0230] In another embodiment, a filter medium (not shown) may be provided that includes at least two membranes, with or without a pathogen-inhibiting layer. The membranes are also suitable for restricting fluid flow. Each membrane may be bonded to the substrate 200 or the pathogen-inhibiting layer. Adhesives used to secure the membranes to the substrate may reduce the membrane's mechanical properties, making them unsuitable for use. However, thermal bonding of the membranes to the substrate 200 may overcome these drawbacks. Additionally, a nonwoven fabric intermediate layer (not shown) may be used as an adhesive layer to mitigate adverse effects on the membranes of the filter medium.

[0231] Optionally, the filter media can restrict fluid flow in a first direction and promote fluid flow in a second direction. In this manner, the filter media can be a two-way filter media that can be inserted into conventional filter cartridges or other filter retention devices. For example, the filter membrane is useful as a water purification filter media or a filter media that can be installed in an air conditioning unit. Other possible uses for the filter media include respirators, masks, water storage tanks, pumps, supply lines, water purification systems, furniture textiles, flooring bases, geotextiles, or any other application where filtration and pathogen suppression are desired.

[0232] In one embodiment, the filter media can be an air filter. Air filters are used to remove contaminants (often solid particles) from the air. Air filters are commonly used in diving air compressors, ventilation systems, air conditioners, and other applications where air quality is important. Air filters include devices that filter air in enclosed spaces such as buildings or rooms, as well as devices or chambers that handle viral materials. Therefore, other items that perform a protective function, such as curtains or screens, can also be considered air filters.

[0233] Air filters are constructed with filter elements made of paper, Styrofoam, cotton, or spun glass fiber. Alternatively, air filters can use electrostatically charged fibers or elements. Mechanical air filters come in four types: paper, foam, synthetic fiber, and cotton. Any substrate can carry a positive or negative charge and attract oppositely charged items. Because most viruses are generally negatively charged, the substrate can be positively charged so that the substrate or its fibers can attract viruses and capture them, which can then be inhibited or destroyed by the ions in the pathogen-inhibiting layer. This is also advantageous because charged fibers can form a more open, and therefore more breathable, substrate, allowing particles, including viruses, to be captured by more than just physical means.

[0234] In another embodiment, two or more substrates 10 can be laminated together. Each substrate may have a unique structure prior to lamination. The resulting article 1 may be configured for medical filtration applications, such as those used in gowns, surgical masks, curtains, etc. The lamination of multiple substrates (coated or uncoated) can be used for many applications and can include multiple pathogen-inhibiting layers with different structures and compositions. Laminating two or more substrates can provide enhanced filtration or germicidal performance. As used herein, the term "disinfection" is understood to refer to cleaning or removing pathogens from a surface by inhibiting, capturing, killing, or otherwise destroying the pathogens. Disinfection can take anywhere from a few seconds to several hours, depending on the characteristics of the pathogen-disrupting layer, the age of the pathogen-disrupting layer, and the surface topography.

[0235] In another embodiment, the article 1 may be a barrier comprising one or more substrates 200 and at least one coating film on the substrates 200. Each substrate 200 may have a unique structure that can be used for any desired functional purpose, such as hydrophobicity, hydrophilicity, electrostatic charge, pathogen inhibition, or other predetermined function. The resulting article 1 may be suitable for medical filtration applications, such as those used in gowns, surgical masks, curtains, etc. Multiple substrates, each coated with one or more coating films, may be used for various purposes, such as forming a protective barrier. The protective barrier may be used for various applications, such as gowns, curtains, bedding, etc. Multiple substrates may be used to provide the article 1 with desired filtration, improved filtration performance, or improved germicidal performance.

[0236] Thus, the present invention provides a more efficient sterilizing filter media for air or liquid filtration. The filter can be configured to provide any desired characteristics, such as low pressure drop and high flow rate during use. The substrate can be configured to provide a sterilizing filter media with a flow rate of 4 mmH2O / cm through the substrate. 2Preferably, the filter material has a breathability that allows for a pressure differential of less than 100 psi. Preferably, the filter material is treated with a pathogen disruption layer. The textile can include at least one pathogen disruption layer, although any number of pathogen disruption layers can be used. Each pathogen disruption layer can be formed from the same material or the same pathogen-inhibiting or pathogen-killing material. Textiles that can be used to disinfect, filter, capture, reduce the movement of, inhibit, destroy, or otherwise prevent the entry of pathogens into the human respiratory system can be used in a layered arrangement or configuration.

[0237] The use of nanoparticles can be a disadvantage in many applications because the bond energy between the substrate and the nanoparticles applied using conventional methods is relatively weak, which can lead to leaching during use. The leaching of silver and other inorganic nanoparticles can pose numerous problems for the wearer, as well as environmental and health impacts. For example, leaching of silver into water systems can lead to algae blooms and disrupt ecosystem balance. Thus, applying nanoparticles within a polymer matrix can increase the overall adhesive strength between the substrate and the deposited nanoparticles compared to traditional solution dipping, padding, or thermal bonding methods known in the art.

[0238] The filter media can be prepared from any suitable natural or artificial material, as described above in connection with at least one embodiment. Preferably, the filter is formed from a generally porous material capable of trapping particles of any given size.

[0239] Polyester fibers can be used to form webs used in filtration devices and media. Polyester blended with polypropylene or cotton can be used to manufacture media. Other fibers can be used in place of cotton in blended articles. Small synthetic fibers called microfibers are used in many types of HEPA (high-efficiency particulate air) filters. High-efficiency air filters may contain a layer of oiled cotton gauze.

[0240] Alternatively, filters can be used to filter liquids. Such filters can be constructed of any suitable fabric, as described above. Filters used to filter liquids can be used to filter drinking water for humans or animals, water for general household use, medical fluids such as plasma or saline, pharmaceutical preparations for injection, or other biological fluids that may come into contact with a patient.

[0241] According to another embodiment, an article of personal protective clothing may be provided, the fibers being coated with a composition of nanoparticles as defined above. The personal protective clothing may be any garment that can utilize the article 1 of the present invention or benefit from a coating or treatment applied in a plasma treatment process to form a pathogen-inhibiting layer. For example, the protective clothing may be a face mask. Such a mask may cover the entire face or a portion of the user's face, preferably the outer area of the wearer's nose and / or mouth.

[0242] A preferred embodiment of the present invention provides a face mask or filter made of a fibrous nonwoven material coated with a pathogen-inhibiting layer by plasma treatment. The pathogen-inhibiting layer may be a composite material having one or more layers bonded or secured together to form an article 1. Article 1 may form at least a portion of a mask or filter. Optionally, a gel, cream, or other solution may be applied to the coated article or articles containing pathogen-inhibiting ions (e.g., silver or copper nanoparticles) that can be used to kill or reduce the activity of at least one pathogen. For example, mixed nanoparticles of zinc oxide (ZnO) and titanium dioxide (TiO2) can be used to inhibit or prevent viral infection. Such mixed nanoparticles of the present invention may also be used in the methods described above, in filters described above, or in protective clothing articles described above.

[0243] In a further embodiment, a method for preparing a filter is provided. The filter can be used for at least one of air and water filtration. The method comprises thermally bonding a silver or copper coated substrate 200 with a thermal adhesive layer, optionally containing a pathogen-retaining medium such as a nonwoven material. The thermal bonding can be performed by at least one process selected from the following group: calendaring, belt calendaring, through-air thermal bonding, ultrasonic bonding, heat bonding, lamination, and autoclaving.

[0244] When article 1 is used to form clothing, the clothing may be selected from the group consisting of face masks (surgical masks, respirator masks), hats, hoods, trousers, shirts, gloves, skirts, boiler suits, surgical gowns (scrubs), etc. Such clothing may be particularly useful in hospitals where infection control is important.

[0245] Preferably, the plasma temperature is below the melting temperature of the article being treated, or the article 1 is exposed to the plasma for a time not sufficient to melt or otherwise plastically deform the article 1. Application of the pathogen-destroying layer may optionally be before the article 1 is exposed to the plasma of module 20, or may be applied while the article 1 is within the treatment region of the module. Preferably, the electrodes 100 are positioned on one side of the article 1, with the article not facing between the electrodes 100 that form the plasma.

[0246] Also disclosed is a method for applying a thin biocidal coating to a nanofiber fabric, which includes depositing a biocidal material such as a film or coating, resulting in a nanoparticle-coated article 1.

[0247] In one embodiment, the method includes the steps of positioning an article relatively below a treatment module; purging the local atmosphere between the article and the treatment module; supplying a plasma fluid to an electrode region of the treatment module, the electrode region including two or more electrodes; igniting a plasma gas to form a plasma in the electrode region; and supplying at least one of a monomer and nanoparticles to the plasma in the electrode region such that the monomer is polymerized by the plasma, and the nanoparticles are fixed to the article by polymerization of the monomer as they form a coating on the article.

[0248] In yet another embodiment, the nanoparticles may be inorganic copper salts. The term "inorganic copper salts" includes inorganic copper compounds that are relatively insoluble in water. Inorganic copper salts are ionic copper compounds, where the cation combines with the anion of another inorganic substance to form the compound. When such salts are brought into contact with water, they typically release copper ions (Cu+ or Cu++). Copper salts with low water solubility, i.e., less than 100 mg / L, and less than 15 mg / L, are preferred. Such preferred copper salts include copper halides, cuprous oxide, and cuprous thiocyanate.

[0249] The term "release of copper cations" generally refers to the provision of copper cations from metal salts suspended by a functionalizing agent to the environment in which the microorganisms currently reside. In one embodiment, release occurs, for example, when copper ions dissolve from the copper halide particles. In another embodiment, release is mediated by a functionalizing agent, such as PVP, which complexes the copper cations until they come into contact with the microorganisms, transferring the cations to the external environment. There are numerous mechanisms for the release of copper cations, and the present invention is not limited to these mechanisms. Another potential antimicrobial effect is the release of anions from the copper halide particles, such as triiodide anion (I3-), a known antimicrobial agent.

[0250] Different salts have different water solubility and can be used to impart a desired release profile of anti-pathogen properties from the coating. For example, sodium chloride, zinc iodide, sodium citrate, sodium acetate, and sodium lactate can be added to a coating containing nitric acid sliver to produce a coating containing water-soluble salts. By adjusting the proportion of salts with different solubilities in the composition, the release rate of the anti-pathogen agent can be varied to provide a short- or long-term release profile over time. These salt materials may have advantages when used as or with wearable articles 1.

[0251] In another embodiment, a silver salt solution can be converted into an aerosol and fed into the plasma region. Silver molecules from the salt can be fractionated, and single silver nanoparticles can be deposited on the article 1. "Silver nanoparticles" refer to particles that are primarily composed of silver metal and have a particle size of about 1 micrometer or less. The silver in the nanoparticles is Ag 0 , Ag 1+ , Ag 2+ It can exist in one or more oxidation states such as

[0252] Relatively "heavy" molecular weight monomers may be required to carry metal particles or metal salts. To be classified as a heavy molecular weight monomer in the context of this disclosure, the molecular weight of a monomer may need to be greater than 160 g / mol.

[0253] In yet another embodiment, the sol-gels can be prepared as high solids solutions and used alone or in blends with other polymers, including at least one selected from the group consisting of natural and synthetic rubber, especially latex rubber, acrylonitrile rubber, PVC plastisols, PVC, polyurethanes, silicones, polycarbonates, acrylates, polyamides, polypropylene, polyethylene, polytetrafluoroethylene, polyvinyl acetate, poly(ethylene terephthalate), polyesters, polyamides, polyureas, styrene-block copolymers, polymethyl methacrylate, acrylic-butadiene-styrene copolymers, polystyrene, cellulose, and derivatives and copolymers of any of the above.

[0254] High solids solutions are particularly advantageous for medical devices; they can be applied to latex rubber by standard foam dipping methods to produce catheters, gloves, and other dipped latex products, and vinyl plastisols can be mixed with the compositions of the present invention to provide dipped and castable antimicrobial PVC devices. Application by a plasma treatment process produces a suitable film and allows for simultaneous drying and curing of the film, which is not achievable by conventional dipping methods.

[0255] The first coating that confers antimicrobial properties can be metallic silver or copper, or a silver, copper, or zinc compound with extremely low solubility in aqueous media. The antimicrobial component can also be an alloy of silver with copper or zinc. The antimicrobial component must release silver, copper, or zinc ions at an effective level of antimicrobial activity. For example, an effective level of antimicrobial activity means a minimum 2-log reduction within 24 hours in a shake flask test, and over an extended period of time, such as months or even years. Components that meet these criteria include silver, silver oxide, silver halide, copper, copper(I) oxide, copper(II) oxide, copper sulfide, zinc oxide, zinc sulfide, zinc silicate, and mixtures thereof. Mixtures of silver and zinc silicate and silver and copper(II) oxide are preferred. The amount of antimicrobial component on the core particles ranges from 0.05 to 20 wt. % based on the particle core material, preferably 0.1 to 5 wt. %. A surprising feature of the present invention is that these powders confer activity at a substantially lower metal loading than that achieved by prior art materials. This is achieved despite the use of a protective coating film to encapsulate the antimicrobial component. In practicing the present invention, the core particles may optionally be pre-coated with alumina in an amount of about 1% to 4% to ensure good antimicrobial properties after precipitation of the antimicrobial component.

[0256] The secondary protective coating can be selected from silica, silicates, borosilicates, aluminosilicates, alumina, aluminum phosphate, or mixtures thereof. The secondary coating acts as a barrier between the antimicrobial particles and the polymer matrix in which they may be incorporated, minimizing interactions with the polymer. This secondary coating is also believed to affect the rate at which the antimicrobial component diffuses from the dispersed particles into the polymer matrix.

[0257] Optionally, a monomer may be present that can be polymerized to form a coating with dispersed nanoparticles or pigments. When the nanoparticles are introduced into the plasma region, they can become activated and bond with the polymer formed in the plasma. This allows the nanoparticles to more easily adhere to the surface and reduces the chance of the nanoparticles becoming detached.

[0258] Some nanoparticles are encapsulated by the polymer, while others are embedded or partially embedded in the polymer coating. Pigments can also be encapsulated, embedded, or partially embedded in the plasma polymer coating. When nanoparticles are encapsulated in the atomized state, they can have an insulating barrier that can reduce the possibility of corona discharges and adverse plasma conditions that would otherwise occur if the nanoparticles were conductive. For example, aluminum and copper nanoparticles are conductive and can cause destabilization in the plasma region when they enter the plasma. Therefore, it is desirable for the particles to be of a size and / or distribution that does not cause adverse plasma conditions, and / or for the nanoparticles to be encapsulated or insulated by the monomer during the plasma polymerization process. Nanoparticles can also be non-conductive until activated by an electrical charge, plasma, or chemical reaction.

[0259] The surface morphology and topography of the pathogen-inhibiting layer may also provide improved benefits related to ion diffusion and pathogen-destructive efficacy. Further morphology and topography may allow the pigment to appear more or less visible and may dull or enhance the luster of the pigment, which may affect the color provided by the pigment.

[0260] The topographical and morphological features of the surface of the first coating film and / or the second coating film can significantly affect the rate of diffusion of ions from the pathogen-inhibiting layer. The relative distance between the nanoparticles and the top surface of the coating can also affect the rate of diffusion of ions from the nanoparticles. Preferably, ions from the nanoparticles are attracted to the exposed surface of the coating to more effectively inhibit pathogens interacting with the article 1.

[0261] The surface roughness of the coating preferably ranges from 0 to 100 nm. The difference in height between the valleys and peaks formed on the surface defines the surface roughness, and the roughness parameter quantifies the vertical spacing of the surface, ignoring the horizontal spacing. A large vertical spacing indicates a rough surface, while a small vertical spacing indicates a smooth surface. Relative surface roughness of 50 nm (median) or greater is considered rough, while a surface roughness of less than 50 nm (median) is considered smooth.

[0262] It will be appreciated that nanoparticles on the coating surface may protrude above the median surface height and increase the overall surface roughness if the proportion of nanoparticles is relatively high.

[0263] In another embodiment, the system can be used to apply further coatings or treatments to article 1, if desired. For example, banknotes are frequently circulated and may have pathogens on their surfaces. As such, it may be desirable to apply a pathogen-inhibiting treatment to the banknotes so that they can be circulated with a reduced risk of pathogen transfer. In this example, banks or other designated locations that handle relatively large volumes of currency can use the system to coat or treat the banknotes or coins to impart a transparent or other essentially non-visible coating to the banknotes and / or coins that can reduce the persistence of pathogens. This may help reduce the likelihood of pathogens remaining on the banknotes or coins.

[0264] Optionally, the system may record the serial number of processed notes, allowing relatively recently processed notes to reduce exposure to further coatings. A record of processed notes may be communicated to the relevant regulatory authorities for monetary purposes.

[0265] In another example, the system can be adapted to treat or retract articles exposed to various conditions, which can help maintain functionality during use. For example, the exterior plastics, wood, and metals of automobiles are commonly exposed to water, dirt, and other debris, which can cause damage, blockages, and other mechanical failures. Therefore, it may be desirable to apply coatings or treatments to these vehicle components to improve their reliability during use. Coatings or treatments may be provided to enable firearms to more easily pass a "mud test" or other similar test in which the automobile component is completely covered with mud, slurry, or high-moisture aggregate. This component is then used to determine whether or not it has clogged or malfunctioned. Thus, having a coating that can prevent unwanted substances from adhering to the surface of a vehicle component can be of great benefit. Coatings applied to the surface of a component may contain nanoparticles to improve the grip of the component (e.g., steering wheel) or may be treated with an antibacterial or antipathogen treatment. Coatings may also have a dull or matte finish to reduce reflection from the coating.

[0266] Because parts may be removed from a vehicle for cleaning or replacement, each part may be treated individually. This can be advantageous when some parts require application of lubricants or other oils to enable smooth operation. In other embodiments, the system is also adapted to apply a lubricant or other coating to the article 1, or portions thereof, that may last for a relatively longer period of time than traditional lubricants. In yet another embodiment, the surface of the part may be treated with an oleophilic coating to improve oil adhesion to the desired part of the vehicle. Other machinery, powered equipment, outdoor facilities, and articles exposed to dirt, mud, water, and other outdoor conditions can benefit from coatings applied by the system 10.

[0267] Although reference has been made to components from vehicles, any other article can be subjected to treatment by system 10 to impart a desired functionality or to deposit nanoparticles onto article 1.

[0268] Items 1 that are commonly touched or handled by people can also be advantageously coated with a coating from system 10. For example, door handles, phones, screen protectors, laptops, portable computers, tablets, bottles, gym equipment, car seats, public transportation seats, airplane interiors, and many other commonly seen items 1. These items 1 may be treated with an anti-pathogen treatment or coating and, optionally, may have an additional coating that can be used to protect the anti-pathogen coating.

[0269] Depending on the size of the nanoparticles and the ability of the system 10 to apply nanometer-thick coatings, the nanoparticles may protrude from the top surface of some coatings. These nanoparticles may be embedded in the coating or may extend substantially throughout the entire thickness of the coating. The nanoparticles may form nodes or ion-emitting nodes that inhibit, destroy, or kill pathogens.

[0270] Optionally, the support for the article 1 can be displaceable relative to the module 20 to achieve a desired distance between the module 20 and the article 1 as it is being treated. In another embodiment, the module is adapted to determine the relative position of the article within the system and can automatically raise or lower the position of the electrodes or raise or lower the module 20 to a desired height based on the treatment being applied and / or the shape of the article 1. The module can also be adapted to perform a sweeping motion within the chamber 15 to conform to the contours of the article 1 being treated. This is particularly advantageous when the article has an undulating, irregular, or non-linear shape, or when the linear shape of the article 1 is at an angle that is not parallel to the module 20.

[0271] In yet another embodiment, the chamber may be purged with ozone (O) gas for a predetermined period of time, which may act as a pathogen suppression medium. The ozone in chamber 15 is then removed and purged with an inert gas suitable for plasma treatment. For example, chamber 15 may be purged with argon gas, which may be the same as the plasma gas supplied to electrode 100. In this manner, two-stage sterilization and coating can be performed by system 10.

[0272] The gas used to purge the chamber 15 can be captured and recycled for use again in the system. Contaminants in the gas recovered by the recycling system can be filtered or removed from the recycled gas. The contaminants can be stored and disposed of off-site or vented to the atmosphere outside the system 10.

[0273] In yet another embodiment, the article 1 may be etched before receiving the coating or during the coating process. The coating may be adapted to melt, dissolve, or deform when exposed to body heat. This is advantageous when nanoparticles embedded within the coating are suitable for cleaning, treating, or sterilizing an area. Such coatings may also be adapted to solidify after melting when the temperature drops below a threshold, allowing the nanoparticles to re-enter the coating or reducing ion diffusion from the nanoparticles. Optionally, the coating is an organic coating that is absorbed by skin or other porous substrates. As an example, bandages and other dressings could be coated with such a coating containing nanoparticles to more effectively treat wounds and potentially infected areas.

[0274] Additionally, passing the monomer through the plasma region and then onto the substrate can allow for fractionation of the monomer and / or nanoparticles within it. This allows for plasma polymerization, which can increase the number of bonding sites compared to traditional UV, thermal, and other coating curing methods. As a result, the applied coating film is generally superior to conventional techniques and can be applied as an overall thinner coating. Thinner coatings offer the benefits of weight reduction, reduced resource consumption, and overall thinner composite materials.

[0275] The system 10 can fully cure or partially cure a coating applied to the article 1. Fully curing a coating can result in a hard, generally non-reactive coating with the desired functionality. Partially curing a coating can also impart the desired functionality, but can also result in a tacky, sticky, reactive, or activated surface. A partially cured coating may be desirable if additional coatings are to be applied to the partially cured coating, or if the coating will react or adhere to another coating or surface. Optionally, the fully cured coating can be activated at a later date with an additional plasma treatment to induce the desired reaction or bonding at the surface.

[0276] Additionally, the coatings that can be applied by system 10 can have a reduced impact on the overall breathability of substrate 200 compared to conventional coating methods, which also helps maintain the softness and hand feel of the pre-coated coating.

[0277] In yet another embodiment, nanoparticle aggregation may also be induced as the passing nanoparticles are fractionated within the plasma region 112. This allows the particles to adhere, bond, combine, or locally contact and function as larger particles. Particles exiting the plasma region 112 are preferably uniformly dispersed on the following article 1. For example, several 50 nm long particles may aggregate to form particles up to 150 nm long. However, it is understood that attractive forces between particles may result in the formation of aggregate structures in a more compact configuration rather than a linear configuration. Other structures may occur naturally depending on the nanoparticle composition, and may cause the formation of agglomerate stacks on the article 1 during deposition. Aggregation can be used to increase the size of deposited particles and aid in the formation of coatings with particles in the nanometer to micron range. The size of the particles in the deposit may be similar or the same as the size of the particles or pigments before application to the article 1, and the crystalline characteristics of the particles may also be retained within the deposit.

[0278] In some embodiments, the anisotropic inorganic network can be intercalated with organic molecules or polymers to provide one- or two-dimensional nanoparticle coatings on the surface of the article 1. A given particle can be arranged in a two-dimensional linear configuration to form a relatively thin surface coating or a molecular planar coating. The linear configuration can be achieved using a magnetic field adapted to align the particles, or by charging the particles so that they self-align in a desired manner. Charging the particles can be achieved during polymerization or during introduction into the plasma region.

[0279] Self-cleaning

[0280] TiO2 particles can be stabilized to provide functionalization. Stabilization is induced by temperature and / or pressure exposure (evacuation method). Coated polyester fabrics can degrade some organic dyes, similar to those found in coffee and red wine, when exposed to UV or sunlight. Evacuation treatment strongly stabilized the TiO2 NPs on polyester, resulting in improved durability of the loaded polyester fabric, but required high temperature treatment, which had to be controlled.

[0281] Optionally, to improve adhesion to cotton substrates, TiO2 anatase nanoparticles were functionalized with 3(trimethoxysilyl)propyl-N,N,N-dimethyloctadecylammonium chloride (QASC) and 3(glycidoxypropyl)trimethoxysilane (GPTS). The TiO2 nanoparticles underwent an acidic hydrolysis process and condensation reaction with QASC. The functionalized TiO2 was dip-coated onto the substrate using a pad-die cure method. Optionally, the substrate surface can be modified prior to coating or particle application.

[0282] It may be desirable to apply the particles to the substrate surface in a solution and then remove the solution in a second step, leaving the particles on the substrate surface. The particles can then be fixed with a binder or coating. The coating is preferably a polymer coating formed by plasma treatment. More preferably, the coating can be formed by a plasma-enhanced chemical vapor deposition (PECVD) process.

[0283] Although reference is made throughout this specification to nanoparticles (NPs), NPs may alternatively be microparticles (FPs), which generally have a higher size in the micron range.

[0284] The use of TiO2 in siloxane coatings may also be used to modify the functionality of the siloxane coatings.

[0285] It will be appreciated that the siloxane coating may be another superhydrophobic coating that loses its superhydrophobic properties upon exposure to UV light. Optionally, TiO2 may be used to convert the superhydrophobic surface to a hydrophilic surface upon continued UV exposure. It will be appreciated that TiO2 can be activated by any type of UV radiation.

[0286] Coating films have been applied by techniques such as layer-by-layer assembly, dip / spray coating, and chemical wet processes to achieve low surface energy hydrophobic surfaces. However, coating is preferably performed by a CVD process, or even a PECVD process, in which coating is performed during plasma exposure.

[0287] Plasma surface treatment allows for the modification of the chemical groups and topography of the treated surface. Surface properties can be modified and improved without affecting the bulk properties of the material. Dry cleaning techniques offer the advantage of being cost-effective and free of harmful chemicals compared to traditional wet surface treatments.

[0288] The gases used to form the plasma are ionized in a predetermined region and used to fractionate precursors or decompose chemicals that enter the plasma.

[0289] The typical temperature of the plasma region is preferably in the range of -100°C to 200°C. More preferably, the temperature of the plasma that may interact with the substrate may be controlled so that the temperature is preferably limited to a temperature below the melting point of the substrate being treated. Preferably, the temperature is below the plastic deformation temperature of the substrate being treated.

[0290] The plasma fluid used in this system includes noble gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe). Optionally, the plasma gas can include other reactive gases, including oxygen, hydrogen, nitrogen, air, fluorine gas (or mixtures thereof), and water vapor. Other fluids can also be used if desired.

[0291] The electrode for striking the plasma can be any suitable electrode, but preferably includes a dielectric barrier or sheath that surrounds or partially covers the conductive core of the electrode. The conductive core can be any conductive material, such as gold, silver, copper, iron, steel, brass, aluminum, or an alloy containing any of the foregoing materials. Other conductive metals can also be used if desired.

[0292] A monomer precursor can be fed into the plasma region to be fractionated and polymerized, and it will be appreciated that while any given monomer may be used, HMDSO may be desired in some particular embodiments.

[0293] Other substances, such as oils, can also be introduced into the plasma zone for polymerization. These include natural oils, synthetic oils, almond oil, orange oil, citrus oils, nut oils, tree oils, tea tree oil, eucalyptus oil, and other selected natural oils. The oil may be vaporized before being introduced into the plasma zone, preferably comprising reactive non-metallic and metallic components. Alternatively, the oil may be aerosolized to carry the pigment or dissolved material into the plasma zone. A dispersant refers to a solvent and the pigment therein that can be applied to the article 1. The article 1 with the applied dispersion can undergo a plasma treatment, similar to that described above, to fix the pigment. Optionally, the substrate surface can be modified before the application of the coating or particles.

[0294] It may be desirable to apply the particles to the substrate surface in a solution and then remove the solution in a second step, leaving the particles on the substrate surface. The particles can then be fixed with a binder or coating. The coating is preferably a polymer coating formed by plasma treatment. More preferably, the coating can be formed by a plasma-enhanced chemical vapor deposition (PECVD) process.

[0295] Nanoparticles may be nanomaterials as natural, incidental, or manufactured materials containing particles, either unbound or as aggregates or agglomerates, where 50% or more of the particles exhibit one or more features in the size range of 1 nm to 100 nm.

[0296] The particle loading on the surface can range from 0.1% to 6% by weight of the applied plasma coating film. Preferably, the coating used to immobilize the particles on the substrate surface is a functional coating. Superhydrophobicity has attracted attention for practical applications such as water repellency, self-cleaning, antifouling, antibacterial properties, and oil-water separation. In one embodiment of the experimental setup, a superhydrophobic coated substrate is prepared by simply immersing it in a solution of TiO nanoparticles and perfluorodecyltriethoxysilane (PFDTS).

[0297] The nanoparticle or pigment coating can be applied to the substrate surface by any desired method, including dip coating, immersion coating, padding, spray coating, or other conventional methods. The liquid, solvent, or carrier medium may be removed, thereby leaving the nanoparticles or pigment on the surface of the treated article. Evaporation, heating, or other removal techniques can be used so that the treated article 1 is left primarily with only the pigment or nanoparticles, and a second-stage plasma coating can lock the nanoparticles or pigment in place.

[0298] Preferably, the particles on the substrate surface are secured to the substrate by a physical coating, which can be a binder or other cement. The applied coating is preferably polymerizable, more preferably applied by a CVD process in which a precursor is fractionated before application to the substrate.

[0299] The coating is preferably formed with hydrophobic functionality to repel liquids before the dye material advances to the substrate. It may be desirable to have at least some of the particles, such as TiO2, in direct contact with the substrate so that they can self-clean upon exposure to UV light and / or oxygen.

[0300] Superhydrophobic coating films have useful properties such as self-cleaning, antifouling, antibacterial, and antifungal properties. Superhydrophobicity is a phenomenon in which the contact angle of a water droplet is 150±1° or more, and is seen in materials found in nature such as lotus leaves, rose petals, butterfly wings, and water striders.

[0301] A typical strategy for fabricating superhydrophobic surfaces is to use hydrophobic materials with low surface tension along with nanoparticles. For superhydrophobicity, many nanoparticles such as TiO2, SiO2, CuS, FeCl2, carbon nanotubes, etc. can be used to create roughness on the surface, which can then be coated with a hydrophobic coating such as plasma coating.

[0302] In the experimental setup shown in Figure 10, a mixture of TiO2 nanoparticles and PFDTS was used to fabricate superhydrophobic coatings on cotton and polyester substrates. The TiO2 nanoparticles are believed to provide surface uniformity and enhance antibacterial activity due to their photocatalytic activity.

[0303] The water contact angle (WCA) of the cotton substrate surface after 10 minutes of HMDSO plasma treatment was 162.78°, while the 1 wt% TiO2 coated substrate achieved 171.31° after 10 minutes of HMDSO plasma treatment, demonstrating good superhydrophobicity. The longer the treatment time, the higher the silicon compound concentration by ATR-FTIR. 21600 kJ / m 2 The K / S value of the sample coated with 1 wt% TiO2 decreased by 75.18% before and after 24 hours of irradiation with light. 1 wt% TiO2 treated with HMDSO plasma showed the same decomposition rate, indicating that HMDSO plasma deposition on the substrate surface does not adversely affect the photocatalytic activity.

[0304] After 2000 or 5000 Martindale rubs, the WCA value of the HMDSO plasma-treated substrate samples decreased to about 140°, which is still highly hydrophobic. HMDSO plasma deposition on the substrate surface significantly aided in the immobilization of nanoparticles after cleaning, and the original photocatalytic activity of the coating was maintained after 40 and 100 minutes of ultrasonic water bathing.

[0305] Self-cleaning: Fabrics, substrates and surfaces retain their original texture and feel. By avoiding regular washing, clothing is modified with self-cleaning particles to maintain clean and odor-free functionality.

[0306] The wettability of a surface when contacted by a water droplet is determined by intermolecular interactions at the three-phase boundary (liquid, solid, and air). The contact angle at the solid-liquid and liquid-air interfaces determines the nature of the interaction. The contact angle is an important aspect in determining whether a surface is hydrophobic or wettable. If the WCA is less than 90 degrees, the surface is called hydrophilic, meaning that water can form a thin film across the surface and completely wet it. On the other hand, if the CA is greater than 150, the surface is considered superhydrophobic, meaning that water beaded up and easily rolled off a slightly inclined surface. Furthermore, if the CA is between 90 degrees and 150 degrees, the surface is classified as hydrophobic.

[0307] The superhydrophobic surface is significantly influenced by the surface topography. The microstructure of the superhydrophobic coating consists of uneven and rough features. Therefore, the water contact angle can be increased, indicating a small interfacial area between the water droplet and the surface. As a result, the surface adhesion is reduced. Furthermore, the microstructure of the superhydrophobic surface is significantly smaller than that of dust or impurities. The self-cleaning mechanism of TiO2 particles may be photocatalytic. These mechanisms are activated by UV radiation such as ultraviolet light and the presence of oxygen.

[0308] The process is a photoreaction accelerated in the presence of a catalyst. This process uses a photoactive material to induce a light-activated catalytic purification function through a chemical change on the surface. The photocatalytic material uses sunlight to decompose organic pollutant molecules. By using sunlight, the photocatalytic material decomposes organic pollutant molecules. Soil, pollutants, and microorganisms are examples of organic pollutants.

[0309] Photocatalytic self-cleaning fabrics use various semiconductor materials, such as titanium dioxide (TiO2), zinc oxide (ZnO), and silica (SiO2). Nanotechnology is being applied to textile treatments because nanoparticles have a high surface area to volume ratio and high energy content. By providing a self-cleaning surface, nanoparticle semiconductor materials add commercial and aesthetic value to textiles.

[0310] Compared to other semiconductors, TiO2 has excellent optoelectronic properties, low-cost production, non-toxicity, and environmental friendliness. TiO2 exists in three distinct crystalline forms: anatase, rutile, and brookite. The rutile phase is the most stable of these three, while the other two are metastable. The metastable phase irreversibly transforms to the rutile phase at high temperatures. TiO2 is a promising photocatalytic hydrophilic material, primarily composed of rutile and anatase phases. It is also well known that the industrial photocatalyst Degussa P-25 TiO2 nanoparticles, composed of 70% anatase and 30% rutile, have excellent photocatalytic activity. TiO2 can be irradiated with an energy source exceeding its band gap (≥3.2 eV).

[0311] It will be appreciated that the combination of hydrophobic functionality and self-cleaning properties can be utilized to provide improved anti-fouling surfaces. As a first example, a hydrophobic coating can provide sufficient surface energy to repel water or other liquids, and preferably also oil. Liquids and stain-causing substances that penetrate the substrate surface are removed by the self-cleaning properties of titanium dioxide upon exposure to a UV light source.

[0312] While particles are preferably applied to the substrate during a PECVD process, it may be beneficial to apply the particles by a dipping process, a spraying process, or other process known in the art in which one or more surfaces of the substrate are coated. It is understood that the solvent or other solution containing the particles may be evaporated prior to applying the polymer coating in a CVD or PECVD process, thereby removing the solution from the substrate surface and leaving the particles. It is understood that "particles" may be substituted for "pigments" herein. Pigments include colorants that are natural or synthetic and may be ground to a predetermined size. Alternatively, it may be beneficial to provide a solution comprising double bonds such that effective polymerization of the solution occurs, leaving the particles embedded in the solution. This may be preferable, as drying the solution may cause the dispersion of particles applied to the substrate to flocculate or reduce uniformity.

[0313] Preferably, increasing the weight percent of TiO2 improves self-cleaning performance. Preferably, the weight percent of TiO2 relative to the solution in which it is dispersed ranges from 0.1 wt% to 5 wt%. It may be desirable for the TiO2 concentration to range from 0.5 wt% to 3 wt% relative to the textile.

[0314] In another embodiment, increasing the weight percent of TiO2 can decrease the hydrophobic performance of the coating, especially after UV exposure. This is desirable for substrates used in UV exposure detection applications, since the hydrophobicity of the substrate may be tested to determine if the substrate has been exposed to UV. This may be useful for packaging that is sensitive to UV light and high temperature exposure.

[0315] Referring to Figure 10, an embodiment of a simplified system that can be used to apply coatings with particles embedded within the final coating is shown. The system consists of a plasma processing module and a plasma region where the plasma coating occurs. The samples processed in the experimental setup were supplied with a polymer generated from HMDSO monomers formed in argon plasma gas.

[0316] Referring to FIG. 11, another embodiment of the K / S change in color relative to the first measured color is shown. The greater the K / S % decrease, the more likely the color change. In this embodiment, the figure shows that substrates with a higher wt. % TiO2 have a higher K / S decrease, potentially making stain removal easier.

[0317] It is worth discussing the basic reaction mechanism by which functional groups are formed. The molecular structure of hexamethyldisiloxane (HMDSO) and the possible fragmentation pathways that occur under plasma action are shown in Figures 12A and 12B. As shown in Figures 12A and 12B, ion bombardment generated by charge accumulation removed side groups such as H and CH3, as well as chain terminators. The presence of Si(CH3)2 chain-propagating units was revealed, as indicated by the stretching of Si-O vibrations in the Si-O-Si domain. By directly fragmenting HMDSO, plasma homogeneous polymerization may promote the disappearance of -CH3 groups. Under the influence of electrons, various reactive fragments are generated, which may further react in the plasma phase to produce groups with higher molecular weights than HMDSO. While plasma phase reactions are homogeneous, plasma surface reactions are heterogeneous. As shown in Figure 12B, chain interconnections can occur via Si-CH2-Si (point 1 in Figure 12B), Si-Si (point 5), and Si-O groups (point 5). It was shown that the absence of H could promote the linkage of adjacent chains. However, all proposed alternatives involved reducing the amount of CH3 in the film. The absorption of OH groups by pendant bonds (Figure 12B, point 3) prevents chain reticulation. Furthermore, once chain crosslinking is possible, depending on the concentration and proximity of the radicals, dangling bonds remain active and react with atmospheric groups when the sample is exposed to air. This mechanism partially explains the occurrence of Si-OH functional groups in organosilicon structures. The incorporation of OH groups during coating deposition could also be due to the environment in the device chamber or the presence of oxygen in the precursor molecules (homogeneous reaction).

[0318] This research experimental process involves a two-step approach to fabricating a self-cleaning coating. In the first step, the sample was immersed in a TiO2(P25)-ethanol solution (three concentrations: 0.1 wt%, 0.5 wt%, and 1 wt%) at a bath ratio of 1:30. Next, the superhydrophobic coating was fabricated using an atmospheric pressure plasma coating system with DBD configuration, 300 V, 130 kHz, and an argon gas flow rate of 40 LPM. The HMDSO gas flow rate was 1.0 L / min, and the HMDSO was heated to 30°C. The samples were treated for 1, 3, 5, and 10 minutes, respectively.

[0319] The chemical composition and morphology of the surface were analyzed by SEM, XRD, and ATR-FTIR. Ultrasonication effectively dispersed TiO2 nanoparticles in ethanol, and dip-coating in the ultrasonic treatment solution successfully produced a uniformly distributed coating on the textile, as evidenced by SEM. XRD diffraction patterns confirmed the presence of polyester fibers with characteristic peaks, as well as TiO2 particles in the anatase and rutile phases. Furthermore, the intensity of the characteristic peaks increased with increasing TiO2 nanoparticle content.

[0320] To investigate superhydrophobicity, we measured water contact angles (WCA) using a tensiometer. Pristine polyester exhibits hydrophobicity, but as the weight ratio of TiO2 nanoparticles to ethanol concentration increases, the hydrophilicity of the coated fabric surface increases. As the HMDSO plasma treatment time increases, the WCA of the fiber surface after 10 minutes of HMDSO plasma treatment reaches 162.78°, while the WCA of the TiO2-coated fiber after 10 minutes of HMDSO plasma treatment reaches 171.31°. SEM images show that the HMDSO plasma-treated TiO2-coated sample exhibits thinner and smaller aggregates, indicating improved surface toughness and superhydrophobicity. Furthermore, the concentration of -CH3 and Si- groups on the polyester surface treated with HMDSO plasma is higher, and the content of silicon compounds increases with longer treatment times, which also contributes to superhydrophobicity.

[0321] To evaluate the photocatalytic self-cleaning effect, the sample was stained with Sudan III-ethanol. After 24 hours of exposure to a solar simulator, the photocatalytic self-cleaning effect was 21,600 kJ / m 2 After 24 hours of light irradiation, the K / S value of the sample coated with 1 wt% TiO2 decreased by 75.18% before and after light irradiation, demonstrating the strongest self-cleaning performance of all concentrations. 1 wt% TiO2 treated with HMDSO plasma showed the same decomposition rate, indicating that HMDSO plasma deposition on the substrate surface does not adversely affect photocatalytic activity.

[0322] To evaluate the durability of the self-healing coating, the superhydrophobic coating was subjected to mechanical testing using the Martindale tester at 2,000 and 5,000 cycles, and further exposed to chemical solutions and UV radiation. The mass of the TiO2-coated and HMDSO plasma-treated TiO2-coated samples remained almost unchanged during the mechanical abrasion tests provided by the Martindale tester. After 2,000 and 5,000 rubs, the WCA value of the HMDSO plasma-treated textile sample slightly decreased to around 140°, but this still represented superhydrophobicity. SEM surface morphology analysis revealed that the superhydrophobic surface of the 1% TiO2-coated sample treated with HMDSO plasma for 5 minutes was smoothed and flattened. As the number of rubs increased to 5,000, more of the smooth outermost layer peeled off. Therefore, the WCA values and SEM images indicated that the HMDSO plasma deposition remained intact on the surface, providing convincing evidence of very high adhesion between the deposition and the polyester fabric. The superhydrophobic surface treated with HMDSO plasma is mechanically robust and long-lasting. Furthermore, the superhydrophobic coating maintains chemical stability even after interaction with ethanol. Regarding resistance to UV irradiation, the HMDSO plasma-treated textile maintains its initial superhydrophobicity at approximately 150°C after 24 hours of simulated light exposure. However, the WCA value of the 1 wt% TiO2 fiber treated with HMDSO plasma dramatically decreased from 150°C to 5°C, indicating that the sample transformed from superhydrophobic to hydrophilic after exposure to simulated sunlight. ATR-FTIR data showed that the functional groups of the HMDSO plasma-treated 1% TiO2-coated sample remained unchanged before and after simulated light exposure, and the silicon concentration did not decrease. Furthermore, it was clear that the morphological characteristics of microscale features, such as microscale cracking and coating delamination, remained unchanged.

[0323] To test the adhesion of TiO2 nanoparticles, samples coated with TiO2 nanoparticles and samples coated with HMDSO plasma-treated TiO2 nanoparticles were washed in an ultrasonic water bath for 40 and 100 minutes, respectively. Regarding the photocatalytic effect, it can be concluded that the Martindale abrasion test did not adversely affect the removal of TiO2 nanoparticles from the surface of the polyester sample. In other words, the 1 wt% TiO2-coated sample treated with HMDSO plasma did not wear off or lose any TiO2 nanoparticles during this test. The photocatalytic effect remained unchanged for each sample. However, ultrasonic water washing was significantly effective in removing TiO2 nanoparticles from the coated sample, adversely affecting the photocatalytic effect. It can be seen that HMDSO plasma deposition on the fiber surface significantly contributes to the fixation of nanoparticles and the retention of the coating's original photocatalytic function after washing.

[0324] This study demonstrates two important self-cleaning features of HMDSO atmospheric-pressure plasma-treated TiO2-coated polyester: (a) a superhydrophobic coating that repels water, and (b) self-cleaning of organic contaminants achieved by the photocatalytic properties of TiO2 nanoparticles under the action of light. The TiO2 nanoparticle coating process is simple and straightforward and does not require high-temperature curing. Furthermore, the excellent quality of HMDSO plasma deposition allows the TiO2 nanoparticles to firmly adhere to the fiber surface, imparting effective persistence and durability to this multifunctional self-cleaning system.

[0325] Fire-resistant or flame-retardant

[0326] Flame retardants can reduce or inhibit the flammability of textile products by suppressing heat release during combustion, reducing flammable volatiles, modifying pyrolysis reactions, forming a fuming char layer, releasing water, releasing spices such as chlorine and phosphorus, or acting as an inhibitor in the gas phase.

[0327] Suitable particles for use in flame-retardant coatings include particles selected from nanoclays, carbon nanotubes (CNTs), layered double hydroxides (LDHs), polyhedral oligomeric silsesquioxanes (POSS), silicon dioxide (SiO2), and metal nanoparticles. Optionally, the SiO2 may be nanosized. Any combination of particles can be used in a single coating. Optionally, the coating may be formed from several layers or different materials, with each layer having a desired thickness or containing desired nanoparticles or pigments.

[0328] Suitable nanoclays are nanoparticles of layered mineral silicates, which are divided into several classes depending on their chemical composition and morphology, such as montmorillonite (MMT) and halloysite.

[0329] The metal nanoparticles may also be metal-based nanoparticles or oxides, such as titanium dioxide (TiO2), zinc oxide (ZnO), aluminum oxide (Al2O3), and the like.

[0330] Preferably, the thickness of the applied coating is at least 100 nm, although it may be more preferable to select a coating in the range of 100 nm to 100 microns for flame retardant treatments or coatings.

[0331] Preferably, the char yield of the substrate is improved by including a flame-retardant coating. The coating preferably includes particles, such as microparticles or nanoparticles. After application of the coating, char yield testing preferably shows an improvement of at least 1% compared to a substrate that has not been treated with the coating.

[0332] The coating thickness can range from 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 relative to the diameter of the particles within the coating.

[0333] It is preferred that the particles in the coating are generally uniform in diameter or size. It will be understood that a particle size distribution may be provided in the coating, the distribution consisting of particle sizes in a known size range, with the remaining particles being larger or smaller than the known size range. For example, the particles in the coating may have 80% by volume of a known particle size, with the remaining 20% being smaller or larger than the known particle size diameter range. For example, the particles in the coating may have 80% by volume of a known particle size, with the remaining 20% being smaller or larger than the known particle size range.

[0334] Optionally, the applied particle coating provides a flame retardant coating or can be used in combination with a flame retardant coating applied via a chemical vapor deposition process, preferably a plasma enhanced chemical vapor deposition process.

[0335] The flame retardant coating particles may be applied to the coating stack or may be distributed uniformly throughout the coating.

[0336] The particles may be deposited on the surface of a substrate to be coated with a functional coating, or may be provided simultaneously with the application of the functional coating to the substrate.

[0337] 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 location. The thickness of the coating may extend to at least 5% of the particle height. Preferably, the particles are encapsulated by the coating.

[0338] Siloxane can be used as part of the coating to compensate for the flame retardancy of the particles.

[0339] Particle sizes suitable for the present disclosure may range from 1 nm to 900 microns. More preferably, the particle size range preferably used within the coating is 10 nm to 200 μm.

[0340] Particle fixation may be desirable in applications where a single use of article 1 is preferred. In such cases, the thickness of the embedding or coating may be less critical than the thickness of the fixation or coating where increased durability is required or where multiple uses are anticipated. For example, clothing coated onto a garment substrate is likely to have higher durability requirements due to the potential for multiple uses. Furthermore, when a pigment is provided in the article, the pigment is adapted to provide a color or range of colors to article 1. This is particularly advantageous for clothing, where it may be desirable to improve the colorfastness of the clothing by permanently fixing the pigment to article 1.

[0341] Although the present invention has been described with reference to particular embodiments, those skilled in the art will recognize that the present invention can be embodied in many other forms consistent with the broad principles and spirit of the invention described herein.

[0342] The present invention and the preferred embodiments described include at least one feature that is particularly applicable industrially.

Claims

1. 1. A coating film for an article, the coating film having an upper side and a lower side, the coating film being applied to at least one surface of the article, the coating film being formed from monomers and nanoparticles that have been passed through a plasma.

2. The substrate of claim 1 , wherein the monomer is at least partially polymerized when introduced into the plasma.

3. The substrate of claim 1 or 2, wherein the nanoparticles and the monomer are a dispersion that is atomized before being introduced into the plasma.

4. The substrate according to any one of claims 1 to 3, wherein the monomer and the nanoparticles are passed through the plasma before being deposited on the article.

5. The substrate according to any one of claims 1 to 4, wherein one or more types of nanoparticles are contained in the coating film.

6. The substrate according to any one of claims 1 to 5, wherein the upper side of the coating film is exposed to the atmosphere.

7. The substrate of any one of claims 1 to 6, wherein the upper side of the coating is configured to contact one or more pathogens.

8. The substrate of any one of claims 1 to 7, wherein the nanoparticles have at least one of pathogen-inhibiting properties and oligodynamic properties.

9. 1. A method of treating an article having a pathogen-inhibiting layer, comprising: placing an article relatively below a processing module; purging the local atmosphere between the article and the processing module; supplying a plasma fluid to an electrode region of the treatment module, the electrode region comprising two or more electrodes; igniting a plasma gas to form a plasma in the electrode region; supplying at least one of a monomer and nanoparticles to the plasma in the electrode region, the monomer being polymerized by the plasma, and the nanoparticles being fixed to the article by the polymerization of the monomer, forming a coating film on the article; A method comprising:

10. 10. The method of claim 9, wherein the nanoparticles are configured to release ions to disrupt the persistence of pathogens in contact with the coating.

11. 11. The method of claim 9 or 10, wherein the nanoparticles are distributed throughout the thickness of the coating film.

12. The method of any one of claims 9 to 11, wherein the processing module identifies an item under the electrodes and activates electrodes corresponding to the size of the item.

13. The method of any one of claims 9 to 12, wherein the nanoparticles are carried to the article by a carrier fluid.

14. The method of any one of claims 9 to 13, wherein gas openings eject the monomer and the nanoparticles into the plasma region and onto the article.

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