System and method for grafting a molecular code onto a material by atmospheric plasma treatment

Abstract

The present disclosure describes a material surface treatment system and method for grafting an encoding substance (e.g., a molecular code) onto a material through a surface treatment process. In some examples, the material is subjected to a plasma discharge containing a molecular code, and the molecular code is grafted onto the material at a molecular level, thereby having little or no effect on the properties of the treated material.

Description

Technical Field

[0001] [Cross - Reference to Related Applications] This application claims the priority and benefit of U.S. Provisional Patent Application No. 63 / 044,861, filed on June 26, 2020, entitled "Systems And Methods For Grafting A Molecular Code Onto A Material By An Atmospheric Plasma Treatment". The entire disclosure of the above - mentioned U.S. application is incorporated herein by reference for all purposes.

Background Art

[0002] Some material surface treatment systems utilize high - voltage electrodes to treat the surface of articles such as foils or films by means of a discharge. Conventional treatment systems are used to modify the properties of the material being processed. However, when adding information to a material, conventional systems are limited to conventional printing methods that are prone to modification, replication, or removal. Thus, as a manufacturer, it would be beneficial to have a system or method for material surface treatment that embeds information on a material in a more indelible manner.

Summary of the Invention

[0003] A system and method for material surface treatment that grafts a codified substance onto a material through a surface treatment process are disclosed. In particular, this system and method utilize electrodes to generate a plasma containing the codified substance, and the codified substance is then grafted onto the material during a plasma surface treatment process.

[0004] These and other features and advantages of the present invention will become apparent from the following detailed description in conjunction with the appended claims.

[0005] The benefits and advantages of the present invention will be readily apparent to those skilled in the art after considering the following detailed description and the accompanying drawings.

Brief Description of the Drawings

[0006]

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[0007] The drawings are not necessarily to scale. Appropriate cases, the same or identical reference numerals are used to refer to the same or identical components.

[0008] The present disclosure describes a material surface treatment system and method for grafting a coded substance (e.g., a molecular code) onto a material through a surface treatment process. In some examples, the material is subjected to a plasma discharge containing the molecular code, and the molecular code is grafted onto the material at the molecular level, thereby having little or no effect on the properties of the treated material.

[0009] In some examples, the material surface treatment system and method for grafting a coded substance includes a vaporizer that receives a solution containing the molecular code. The vaporizer produces a vapor having the molecular code, and this vapor is then exposed to an electrode, and a plasma is generated from the ionization process gas and the vapor by a discharge. Thereafter, the plasma is applied to the material near the electrode and is adapted to graft the molecular code onto the material by the plasma.

[0010] A material surface treatment system can be equipped to process a variety of materials (e.g., plastics such as polyethylene and polypropylene) having surfaces with low surface tension that inhibit bonding by surface treatment, such as printing ink, coating, and / or adhesive. The material surface treatment system is utilized to modify the properties of specific materials (e.g., plastics and / or flexible substrates) for specific applications (e.g., ink, coating, adhesive, and / or lamination). For example, plastic films generally require some type of surface treatment to achieve proper chemical bonding with ink, adhesive, etc. This is in contrast to porous materials such as paper where ink can penetrate the medium.

[0011] Using such systems and methods, a variety of materials (e.g., polyethylene, polypropylene, nylon, vinyl, PVC, PET, metallized surfaces, foils, paper, and paperboard stock) can be effectively processed.

[0012] To provide the desired material properties of such materials, various techniques are implemented. For example, corona treatment is a surface treatment that utilizes a relatively low-temperature corona discharge to change the surface properties of a material. Corona treatment using one or more electrodes provides the desired adhesion properties at a reasonable cost. The corona electrode is effective in generating a high-voltage discharge and modifying the surface energy of the processed material (e.g., plastic, paper, foil, etc.).

[0013] As another example, there is plasma treatment in which a gas is injected into an electrode discharge to treat the material surface. For example, depending on the material, some materials are more likely to undergo plasma treatment than corona treatment to achieve desired material properties such as bonding properties.

[0014] Plasma treatment is often associated with increased cost and complexity, such as the use of more complex electrodes and more process control compared to corona treatment. Therefore, there are limitations to implementing plasma treatment on a larger scale in the industry. However, depending on the material, there are some materials that react more favorably to plasma treatment than corona treatment (e.g., fluoropolymers, polypropylene, etc.).

[0015] As disclosed herein, both a corona treatment system and a plasma treatment system that utilize a corona electrode and a plasma electrode respectively can be utilized to graft a coded substance (e.g., a molecular code) onto a material through a surface treatment process as provided in the following examples.

[0016] The disclosed material surface treatment system and method are advantageously configured to graft a molecular code onto a material without affecting the desired properties of the treated material. In addition, the material surface treatment system and method can make it extremely difficult to introduce, modify, or remove coded information and provide strong protection to the material manufacturer because the molecular code is incorporated into the material at the molecular level.

[0017] In the disclosed examples, the material surface treatment system includes a vaporizer that receives a solution containing a molecular code and produces a vapor having the molecular code, and an electrode that generates a discharge to produce a plasma composed of an ionized process gas and the vapor, applies the plasma to a material near the electrode, and grafts the molecular code onto the material by applying the plasma.

[0018] In some examples, the material surface treatment system further includes a ground roll configured to engage the material, and the material is subjected to the plasma discharged from the electrode when the plasma is attracted to the ground roll, and the ground roll is electrically connected to a reference voltage.

[0019] In an example, one or more properties of the material are modified as a result of applying plasma. In an example, the material is one of a polymer, a synthetic woven and / or non-woven fabric, a natural fiber woven fabric, a filament, a thread, an elastomer, or a metal.

[0020] In some examples, the ionizing process gas forms a hydroxy group, a carboxyl group, a carbonyl group, or an amine. In some examples, a non-ionizing process gas is introduced into a vaporizer, and the vaporizer comprises a heater that heats the non-ionizing process gas and a molecular solution to combine or evaporate the non-ionizing process gas and the molecular solution.

[0021] In some examples, the electrode includes one of a plasma electrode or a corona electrode. In some examples, the electrode is connected to a power source configured to provide a current to activate the electrode.

[0022] In some examples, the material is a wound web. In an example, the material is a flat structure. In an example, the material is a polyhedron.

[0023] In some of the disclosed examples, a material surface treatment system is configured to process a flat object. The system includes a vaporizer that receives a solution containing a molecular code and produces a vapor having the molecular code, an electrode that generates a discharge to produce a plasma composed of an ionizing process gas and the vapor, and one or more rollers that transport the flat object toward the electrode to apply the plasma to the material of the flat object near the electrode, and graft the molecular code to the material by applying the plasma.

[0024] In some examples, the material surface treatment system further includes a ground block on the opposite side of the electrode with respect to the material, and the material is subjected to the plasma discharged from the electrode when the plasma is attracted to the ground block, and the ground block is electrically connected to a reference voltage. In an example, one or more properties of the material are modified as a result of applying plasma.

[0025] In some of the disclosed examples, the material surface treatment system is configured to process an object having a non-uniform geometry. The system includes a vaporizer that receives a solution containing a molecular code and produces a vapor having the molecular code, an electrode that generates a discharge to produce a plasma composed of an ionized process gas and the vapor, and a nozzle that applies the plasma to the material of an object near the electrode, wherein the application of the plasma grafts the molecular code onto the material.

[0026] In some examples, the electrode extends into the body. In an example, the system further includes a filter that serves as a partial barrier between a first volume disposed within the body and configured to receive the vapor and a second volume that includes one or more dielectric elements. In an example, the second volume is configured to produce a plasma by supplying the vapor to a discharge between the electrode and the dielectric element.

[0027] In some examples, the material surface treatment system further includes a non-linear conveyor configured to apply the molecular code by movement of the nozzle around the material. In some examples, the electrode includes one of a plasma electrode or a corona electrode.

[0028] As used herein, the term "power source" refers to any device capable of supplying power to a material processing system when power is applied thereto. This includes, but is not limited to, inverters, converters, resonant power sources, quasi-resonant power sources, etc., as well as control circuitry and other associated auxiliary circuitry. The term can include energy storage devices and / or circuitry and / or connections for drawing power from various external power sources.

[0029] As used herein, "circuit" or "circuit section" includes any analog and / or digital components, power and / or control elements, such as microprocessors, digital signal processors (DSPs), software, etc., discrete and / or integrated components, or portions and / or combinations thereof.

[0030] As used herein, "power conversion circuit section" and / or "power conversion circuit" refers to a circuit section and / or electrical component that converts power from one or more first forms (e.g., power output by a generator) to one or more second forms having any combination of voltage, current, frequency, and / or reactive characteristics. The power conversion circuit section can include a safety circuit section, an output selection circuit section, a measurement and / or control circuit section, and / or any other circuit providing appropriate features.

[0031] As used herein, the terms "first" and "second" may be used to enumerate different components or elements of the same type and do not necessarily imply any particular order.

[0032] FIG. 1 shows a material processing system 10 including a discharge electrode 14 electrically connected to a power source 12. The electrode 14 can be disposed within a housing 24, which can create a controlled environment (e.g., controlled pressure, temperature, contamination by by-products, etc.) for performing a material processing process. In some examples, a ground roller 16 (e.g., a grounded bare roll having a path to ground or another reference voltage) is utilized and disposed near the electrode 14 to pass a web of material 22 (e.g., fibers, paper, plastic, film, etc.) through the plasma 32 generated by the discharge of the electrode 14 for processing.

[0033] In some examples, the discharge electrode 14 consists of a dielectric tube (e.g., ceramic) or a stainless steel electrode, and the grounding roller 16 consists of a stainless steel roller or a grounding roller covered with ceramic or glass. Any of the rollers cooperate to uniformly distribute the high voltage charge along the length of the electrode 14.

[0034] The power supply 12 that provides the power input can include a high voltage transformer, a power converter, and / or a power supply (e.g., a commercial power supply). In some examples, the power supply 12 provides a power density applied to the discharge electrode 14 of approximately 10 watts per square meter to 110 watts per square meter, and in some examples, approximately 20 watts per square meter to 60 watts per square meter, although other ranges are also contemplated.

[0035] As shown, the system 10 includes a vaporizer or flash evaporator 26 that receives one or more inputs such as gas or fluid. In the example of FIG. 1, the input includes a solution containing a molecular code and / or a process gas. The molecular code can include information regarding a particular trait that can be grafted onto the material 22 at the molecular level. The information can include, for example, location, entity, process, which can later be revealed by analysis of the chemical composition of the material.

[0036] In some examples, the molecular code solution consists of approximately 20 parts to 110 parts of deionized water per part of the molecular code solution, and in some examples, approximately 40 parts to 80 parts of deionized water per part of the DNA solution, although other ranges are also contemplated. In some examples, the molecular code solution is introduced into the vaporizer 26 at a rate of approximately 0.1 milliliters per centimeter of electrode length per minute to 1.0 milliliters per centimeter of electrode length per minute, and in some examples, approximately 0.3 milliliters per centimeter of electrode length per minute to 0.8 milliliters per centimeter of electrode length per minute, although other ranges are also contemplated.

[0037] In some examples, the process gas can include a mixture of different gases, including a mixture of nitrogen and oxygen. For example, the mixture of process gas can include nitrogen at a concentration of approximately 99% to 80%, in some examples approximately 97% to 88%, although other ranges are envisioned. The mixture of plasma gas can include oxygen at a concentration of approximately 20% to 1%, in some examples approximately 12% to 3%, although other ranges are envisioned. In some examples, when the process gas or mixture gas is ionized, it can form certain functional groups such as, by way of a non-limiting list of examples, hydroxy groups, carboxyl groups, carbonyl groups, or amines.

[0038] Vaporizer 26 receives vapor 28 having a molecular code and / or process gas, which is then conveyed via conduit 27 (e.g., via a fan, pump, etc.) to the region between electrode 14 and ground roller 16. In an example, vaporizer 26 includes a heater 34 that generates heat to convert the input to vapor 28. For example, vaporizer 26 can heat the input at a temperature of approximately 100 degrees Celsius to 250 degrees Celsius, in some examples approximately 180 degrees Celsius to 220 degrees Celsius, although other ranges are envisioned.

[0039] In some examples, by using one or more sensors (e.g., flow meters, pressure sensors, etc.) or valves, the rate and / or amount at which the molecular code solution and / or process gas enters the flash evaporator 26 and / or the housing as vapor 28 can be monitored and / or controlled. Thus, when the molecular code solution vaporizes, vapor 28 can be conveyed by the process gas to electrode 14 at a flow rate of approximately 1 liter per centimeter of electrode length per minute to 10 liters per centimeter of electrode length per minute, in some examples approximately 2 liters per centimeter of electrode length per minute to 5 liters per centimeter of electrode length per minute, although other ranges are envisioned.

[0040] When the vapor 28 reaches the electrode 14, a plasma 32 is generated by high-voltage discharge to ionize the process gas and the molecules of the molecular code. For example, the functional groups (e.g., hydroxy groups) of the ionized molecules in the process gas serve as binders for the molecular code, and the ionized molecules are then attracted to the grounded roll 16, and the plasma 32 having the molecular code is attracted to the material 22. Also, the plasma 32 propagates the collisions of the ionized molecules. As a result, the molecular code is grafted onto the material 22. For example, the molecular code is grafted at the molecular level, thereby having little or no effect on the properties of the treated material. In particular, during the material surface treatment process, one or more properties of the material can be modified, such as for adjusting the porosity, adhesion capacity, or strength of the material, as a non-limiting list of properties. An exemplary material treatment process may produce one or more by-products 30 (e.g., water vapor, non-reactive gas, ozone), which can be removed from the treatment area as exhaust and / or for additional treatment.

[0041] In the disclosed examples, the material is one of a polymer, synthetic woven and / or non-woven fabric, natural fiber woven fabric, filament, thread, elastomer, or metal, as a non-limiting list of properties. In any case, the material can be presented for treatment in various configurations. For example, the material may be presented as a substantially flexible web, film, foil, etc., and the conveyance of the material is adapted to be transferred from the supply roll 20 to the take-up roll 18. In some examples, the material is presented as a substantially flat, e.g., rigid, semi-rigid, or flexible sheet, plate, board, etc. (see, for example, the exemplary system of FIG. 2). In some examples, the material is presented with a non-uniform geometry, and the application of the molecular code can be carried out by using a non-linear conveyor and / or a movable electrode configuration (see, for example, the exemplary system of FIG. 3). In each exemplary configuration, the system and method are designed to apply the molecular code according to the disclosed techniques.

[0042] In some examples, the materials processing process is controlled by one or more programs executed by one or more control circuits, such as on an integrated or remote computing platform. For example, the control circuit, control circuitry, and / or controller can include digital and / or analog circuitry, discrete and / or integrated circuitry, microprocessors, digital signal processors (DSPs), field programmable gate arrays (FPGAs), and / or other logic circuitry, and / or associated software, hardware, and / or firmware. The control circuit or control circuitry can be located on one or more circuit boards that form part or all of the controller and is used to control the materials processing process. The control circuit can include memory for storing information such as program instructions executed by the control circuit, and the memory can include volatile memory devices and / or non-volatile memory devices and / or other storage devices.

[0043] Materials processed by the processes disclosed herein can be tested to reveal embedded coded information. For example, the materials can be subjected to one or more chemical test techniques (e.g., electrophoresis, chromatography, spectroscopy, mass spectrometry, etc.), thereby reverse-compiling the information contained within the molecular code. Such test results indicate the presence or absence of the molecular code.

[0044] FIG. 2 shows another exemplary material processing system 10 configured to process a substantially flat article for treatment. As shown in FIG. 2, the transport system includes one or more of a platform and / or a belt 41 on which a material structure 36 (e.g., a substantially flat structure, e.g., a rigid, semi-rigid, or flexible sheet, plate, board, etc.) is placed when traversing the region between the electrode 14 and the ground block 38. In some examples, the platform 41 is driven by one or more rollers 40, 42 and operates as a conveyor for the material structure 36. In additional or alternative examples, the material structure 36 is placed on one or more rollers 40, 42 and is transported through the housing 24 without the assistance of the platform 41.

[0045] FIG. 3 provides yet another exemplary material surface treatment system 50 configured to process an object 70 having a non-uniform geometry. For example, the object 70 can be a three-dimensional object having a plurality of surfaces, and one or more of the surfaces are treated to graft a molecular code to the material of the object 70. Thus, the application of the molecular code can be carried out by the use of a non-linear conveyor and / or by the movement of the electrode around the article and / or by the movement of the article around the electrode.

[0046] In the example of FIG. 3, the power supply 12 provides power to an electrode 54 extending within the body 52. A filter 60 serves as a partial barrier between a first volume 76 configured to receive vapor 64 and disposed within the body 52 and a second volume 78 including one or more dielectric elements 62. The vapor 64 is conveyed from the vaporizer 26 via a conduit 56, and the vapor 64 includes a molecular code and / or a process gas. The vapor 64 is introduced into the second volume 78 and subjected to a discharge between the electrode 54 and the dielectric element 62, thereby creating a plasma 66 that is applied to the object 70 via a nozzle 58. In this way, the molecular code is grafted onto the region of the material of the object 70 that is exposed to the plasma 66.

[0047] In some examples, a precursor gas, such as nitrogen, can be introduced into the main body 52 via the conduit 74. Additionally or alternatively, the system 50 can be fully or partially surrounded within the housing. In some examples, the object 70 can be grounded either via a direct path to ground or via a connector to ground or a reference voltage.

[0048] FIG. 4 provides a flowchart showing an exemplary instruction 100 that can be executed by the exemplary material surface treatment system of FIGS. 1-3 to graft a molecular code onto a material, according to an aspect of the present disclosure. At block 102, a solution containing the molecular code is received in an evaporator or vaporizer or the like. At block 104, the solution and the processing gas are evaporated and introduced to the electrodes at block 106. At block 108, the vapor is ionized to create a plasma, and at block 110, the plasma is applied to the surface of the material to graft the molecular code onto the material.

[0049] As used herein, "and / or" means any one or more of the items in the list connected by "and / or". As an example, "x and / or y" means any of the three elements of the set {(x), (y), (x, y)}. In other words, "x and / or y" means "one or both of x and y". As another example, "x, y and / or z" means any of the seven elements of the set {(x), (y), (z), (x, y), (x, z), (y, z), (x, y, z)}. In other words, "x, y and / or z" means "one or more of x, y and z". As used herein, the term "exemplary" serves as a non-limiting example, instance or illustration. As used herein, the term "for example" begins a list of one or more non-limiting examples, instances or illustrations.

[0050] Although the present method and / or system have been described with reference to certain specific embodiments, those skilled in the art will understand that various changes can be made and equivalents can be substituted without departing from the scope of the present method and / or system. In addition, many modifications can be made to adapt the teachings of the present disclosure to specific situations or materials without departing from the scope of the present disclosure. For example, the disclosed example systems, blocks, and / or components can be combined, divided, rearranged, and / or otherwise changed. Therefore, the present method and / or system are not limited to the specific embodiments disclosed. Instead, the present method and / or system include all embodiments that fall within the scope of the appended claims, literally or under the doctrine of equivalents. Some embodiments of the present invention are described in the following items [1]-

[20] . [1] A material surface treatment system, A vaporizer that receives a solution containing a molecular code and produces a vapor having the molecular code, the vaporizer; An electrode that generates a discharge to produce a plasma composed of an ionization process gas and the vapor, applies the plasma to a material near the electrode, and grafts the molecular code to the material by the application of the plasma, the electrode; A material surface treatment system comprising. [2] The material surface treatment system according to item 1, further comprising a ground roll configured to engage with the material, wherein the material is subjected to the plasma discharged from the electrode when the plasma is attracted to the ground roll, and the ground roll is electrically connected to a reference voltage. [3] The material surface treatment system according to item 1, wherein one or more properties of the material are modified as a result of applying the plasma. [4] The material surface treatment system according to item 1, wherein the material is one of a polymer, a synthetic woven fabric and / or a non-woven fabric, a natural fiber woven fabric, a filament, a yarn, an elastomer, or a metal. [5] The material surface treatment system according to item 1, wherein the ionization process gas forms a hydroxy group, a carboxyl group, a carbonyl group, or an amine. [6] A non-ionized process gas is introduced into the vaporizer, and the vaporizer comprises a heater that heats the non-ionized process gas and the molecular solution to combine or evaporate the non-ionized process gas and the molecular solution. The material surface treatment system according to item 1. [7] The material surface treatment system according to item 1, wherein the electrode includes one of a plasma electrode or a corona electrode. [8] The material surface treatment system according to item 1, wherein the electrode is connected to a power source configured to provide a current to activate the electrode. [9] The material surface treatment system according to item 1, wherein the material is a wound web.

[10] The material surface treatment system according to item 1, wherein the material is a flat structure.

[11] The material surface treatment system according to item 1, wherein the material is a polyhedron.

[12] A material surface treatment system configured to process a flat object, A vaporizer that receives a solution containing a molecular code and produces a vapor having the molecular code, the vaporizer; An electrode that generates a discharge to produce a plasma composed of an ionization process gas and the vapor, One or more rollers that convey the flat object toward the electrode and apply the plasma to the material of the flat object near the electrode, and graft the molecular code to the material by applying the plasma, A material surface treatment system comprising:

[13] The material surface treatment system according to item 12, further comprising a ground block on the opposite side of the electrode with respect to the material, and the material is subjected to the plasma emitted from the electrode when the plasma is attracted to the ground block, and the ground block is electrically connected to a reference voltage.

[14] The material surface treatment system according to item 12, wherein one or more properties of the material are modified as a result of applying the plasma.

[15] A material surface treatment system configured to process an object having a non-uniform geometric shape, A vaporizer that receives a solution containing a molecular code and produces a vapor having the molecular code, An electrode that generates a discharge to produce a plasma composed of an ionization process gas and the vapor, A nozzle that applies the plasma to the material of the object near the electrode, and grafts the molecular code to the material by applying the plasma, A material surface treatment system comprising:

[16] The material surface treatment system according to item 15, wherein the electrode extends into the body.

[17] The material surface treatment system according to claim 16, further comprising a filter that serves as a partial barrier between a first volume portion disposed in the body and configured to receive the vapor and a second volume portion including one or more dielectric elements.

[18] The material surface treatment system according to item 17, wherein the second volume portion is configured to produce the plasma by supplying the vapor to a discharge between the electrode and the dielectric element.

[19] The material surface treatment system according to item 15, further comprising a non-linear conveyor configured to apply the molecular code by moving the nozzle around the material.

[20] The material surface treatment system according to item 15, wherein the electrode includes one of a plasma electrode or a corona electrode.

Claims

**Claim 1** A material surface treatment system configured to process an object having a non-uniform geometry, a vaporizer that receives a solution containing a molecular code and produces a vapor having the molecular code, an electrode that generates a discharge to produce a plasma composed of an ionization process gas and the vapor, a nozzle that applies the plasma to the material of the object near the electrode, and grafts the molecular code to the material by the application of the plasma, a non-linear conveyor configured to apply the molecular code by movement of the nozzle around the material comprising a material surface treatment system. **Claim 2** The electrode extends into the body, the material surface treatment system according to claim 1. **Claim 3** The material surface treatment system according to claim 2, further comprising a filter that serves as a partial barrier between a first volume portion disposed in the body and configured to receive the vapor, and a second volume portion including one or more dielectric elements. **Claim 4** The second volume portion is configured to produce the plasma by supplying the vapor to a discharge between the electrode and the dielectric element, the material surface treatment system according to claim 3. **Claim 5** The electrode includes one of a plasma electrode or a corona electrode, the material surface treatment system according to claim 1.

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