JP2014527257A - A method and apparatus for surface treatment of materials using a plurality of coupled energy sources. - Google Patents

Abstract

At least two material treatments such as (i) atmospheric pressure (AP) plasma, (ii) ultraviolet (UV) laser directed to said plasma and optionally processed material in the processing region (124) Implemented by two energy sources. The precursor (323) may be supplied before processing, and the finishing material (327) may be supplied after processing. The electrodes (e1, e2) that generate the plasma comprise two spaced rollers (212/214; 412/414; 436/438). The nip rollers (416/418; 436/438) adjacent to the electrode rollers (412/414) define a semi-air tight cavity (440) and may have a metal outer layer (437/439). .

Description

This application claims the benefit of the filing date of US application 61 / 501,874 (filed Jun. 28, 2011).
The present invention relates to the surface treatment of materials and various substrates, more particularly fabrics, and more particularly, a plurality of various energy sources combined, typically one of the energy sources is atmospheric pressure plasma. (AP), which relates to the processing of materials.

Smart fabric development improves various properties such as advanced plasma technology, microwave energy sources, and in some cases stain resistance, waterproofing, fastness to color and other characteristics that can be obtained through chemical processing Therefore, it is attracting attention as an active region.

Atmospheric pressure plasma treatment (APT) improves the properties of the surface of the fiber, such as hydrophilicity, without affecting the internal properties of the fiber. It can be used to improve surface properties, improve adhesion, wettability, printability, dyeability, and reduce material shrinkage.

Atmospheric pressure plasma (ie, AP plasma or atmospheric pressure plasma) is a name used in special cases where the pressure in the plasma is approximately the same as the pressure in the ambient atmosphere. AP plasma has an outstanding technical significance. This is because a high-cost reaction vessel for maintaining a pressure level different from the external atmospheric pressure is not required as compared with low-pressure plasma and high-pressure plasma. Also, in many cases, AP plasma can be easily incorporated into a production line. Various types of plasma excitation are possible, including AC (alternating current) excitation, DC (direct current) excitation, low frequency excitation, radio frequency excitation, and microwave excitation. Here, only AP plasma by AC excitation has gained remarkable industrial significance.

In general, AP plasma is generated by alternating current excitation (corona discharge) and a plasma jet. In a plasma jet, a pulsed current arc is generated by a high voltage discharge (5-15 kV, 10-100 kHz) in the plasma jet. A process gas, such as oil-free compressed air flowing through this discharge region, is excited and converted to a plasma state. This plasma then reaches the surface of the material to be processed through the jet head. This jet head is at the surface potential, thus largely suppressing the potential carrying portion of the plasma stream. In addition, the jet head determines the geometry of the outgoing beam. Multiple jet heads are used to interact with corresponding regions of the substrate being processed. For example, sheet material having a processing width of several meters can be processed by a jet train.

Atmospheric pressure and vacuum plasma methods are used to clean and activate material surfaces for adhesion, printing, painting, polymerization, and other functional or decorative coatings. Atmospheric pressure processing is suitable for continuous processing of materials compared to vacuum plasma. Other surface treatment techniques use microwave energy to polymerize the precursor coating.

The present invention aims to provide improved techniques for the treatment of materials (such as surface treatments and modifications), such as a substrate, more specifically a fabric (woven fabric, knitted fabric, non-woven fabric). And a wide range of high-voltage generated plasma (such as atmospheric pressure plasma (AP)) and various additional energy sources (laser irradiation) In addition to the surface, the core of the material being processed can be changed, and gases and precursors introduced in a dry environment can be used. Various energy source combinations are disclosed.

Embodiments of the present invention broadly use industrial fabrics and others using at least two combined energy sources that interact with each other, such as an atmospheric pressure (AP) plasma generated by a laser and a high voltage. And a method and apparatus for processing and producing a plurality of materials.

The techniques described herein can be readily incorporated into an automated dough material processing system. Functionality is obtained through non-aqueous cleaning such as etching and ablating, activation by radical generation on the surface, and also by selectively increasing or decreasing desired functional properties simultaneously. Properties such as hydrophobicity, hydrophilicity, flame retardancy, antibacterial properties, shrinkage reduction, fiber refining, water repellency, low temperature dyeing, improved dye uptake and dyeing fastness, such as the generation of radicals on the surface of the material Realized or enhanced and increased or decreased by processes that generate chemical and / or morphological changes. A coating of material can be applied and processed, such as a nanoscale coating of advanced material composition.

By combining (hybridizing) atmospheric pressure plasma energy with one or more additional (second) energy sources such as lasers, x-rays, electron beams, microwaves or various other energy sources A more effective (commercially practical) energy environment for processing is created. The second energy source may be applied in combination (cooperating, simultaneously) with atmospheric pressure plasma energy to obtain the desired properties and / or in succession (side by side) with atmospheric pressure plasma energy. (Optional) may be applied to obtain the desired properties.

The second energy source acts on a separately generated plasma plume to create a more effective and energetic plasma environment and, optionally, on the surface of the material undergoing this hybrid treatment. Has the ability to act directly on the core.

The techniques disclosed herein include, but are not limited to, processing of dough (both organic and inorganic), paper, synthetic paper, plastic, and other similar materials typically in flat sheet form (yar). Applicable. The technology disclosed in this specification can be applied to extrusion of plastic or metal, rolling, injection molding, spinning, cursing, weaving, glass forming, substrate etching and cleaning, and processing of coating with any substance. In particular, the present invention can be applied to any material processing technique. Rigid materials such as glass flat sheets (such as those used in touch screens) can also be processed by the techniques disclosed herein.

In one aspect, the present invention provides a method for treating a substrate (102, 402, 404),
Generating a plasma in a processing region (124) comprising two spaced apart electrodes (e1 / e2; 212/214; 412/414; 452/454);
Directing at least one second energy source different from the first energy source to the plasma to interact with the plasma to obtain a hybrid plasma;
The hybrid plasma is allowed to interact with the substrate in the processing region (124).

In another aspect, the invention includes an apparatus for processing materials (100, 400A, 400B, 400C, 400D, 400E, 400F, 400G), the apparatus comprising:
Two spaced electrodes (e1 / e2; 212/214; 412/414) that generate plasma in the processing region (124);
One or more lasers (130) that direct one or more corresponding beams (132) to the processing region and interact with at least one of the plasma and the material being processed;
It has.

In a further aspect, the invention relates to the use of the apparatus described herein for treating a dough substrate.

In another aspect, the present invention relates to a dough material obtained by the method described herein.

In yet another aspect, the invention relates to a method for generating a plasma for material processing.

The effects of the present invention include, but are not limited to, a method of generating a more energetic and effective plasma for cleaning and activating the surface for further processing and finishing. For example, ultraviolet (UV) laser irradiation, which can be continuous wave (CW) or pulsed, combined with electromagnetically generated atmospheric pressure plasma, creates a more highly ionized energetic reaction environment for surface treatment. Generate. The resulting hybridized energy has an effect that is greater than the sum of the individual parts. Pulsed laser energy is used to drive the plasma,
Waves are generated and laser energy is applied to the substrate to promote the plasma waves from which the energy was obtained and to strike the waves against the sandy beach.

The promoted, more energetic plasma begins to generate radicals on the surface of the fiber or treated substrate and attaches ionized groups to the radicals that have begun to be generated. The attachment of functional groups such as carboxyl, hydroxyl or others that give increased polar properties to the surface results in greater hydrophilicity and other desirable functional properties.

The present invention advantageously combines energy sources in a controlled atmospheric environment where a material substrate is present. The end result is transformation and material synthesis on the substrate surface, which will change physically as opposed to simply being coated.

In the illustrated embodiment, radio frequency RF plasma extends across the width of the process window and is generated in an envelope (ie, cavity or chamber) formed between rotating and driven rollers. The The generated plasma field is consistent across the width of the processing region and operates at atmospheric pressure. A high power ultraviolet (UV) laser is provided to interact with the plasma and / or the substrate being processed. The beam from the laser is formed to have a rectangular cross section that exhibits a consistent power density throughout the processing region. A gas delivery system may be used to combine any combination of multiple (eg, four) environmental gases and precursors into a single feed that settles in a hybrid plasma chamber. In addition, a spray or mist delivery system may be provided that can apply a thin, consistent layer of sol-gel or processing accelerator to the material being processed, whether pre-treated or post-treated.

The process of combining plasma and photonics (such as a UV laser) is dry, performed at atmospheric pressure, and uses a safe and inert gas (such as nitrogen, oxygen, argon, carbon dioxide). The system by changing the power intensity of the laser and plasma and adding environmental gases and sol-gels and / or changing other organic and inorganic precursors, ie changing the recipe Will be able to generate a wide variety of processing applications.

There are a number of applications in processing, including cleaning, conditioning, and material performance enhancement.
For cleaning, the laser increases the effective power of the plasma and acts independently on the substrate material.
For conditioning substrate materials for secondary treatments such as dyeing, the fiber surface is ablated in a controlled manner, increasing the hydrophilicity of the material (such as a dough material). Furthermore, by introducing an environmental gas into the processing zone of the system, chemistry is generated on the surface of the material (eg, dough), thereby reacting with the dyeing media to provide more efficient dye penetration, or more Chemistry that results in a strong coloring process or reduced dyeing temperature is obtained. For example, adjusting the fibers of the fabric provides a more controlled uptake of chromium oxide dye and improves the strength of the resulting black. Therefore, this process has the potential to reduce the chemical components of the dye, reducing the negative impact on the environment and processing costs.
For performance enhancement, the process acquires material synthesis at the surface of the substrate. By varying the frequency and power intensity of the laser and plasma and introducing other materials into the processing environment, the system ablates the surface of the substrate, and a series of chemical reactions between the substrate and the ambient gas occur. A new material is synthesized on the surface of the fabric web fibers.

Reference will now be made in detail to the disclosed embodiments, some non-limiting examples of which are illustrated in the accompanying drawings. These drawings are generally conceptual diagrams. Some elements in the drawings are exaggerated and some elements may be omitted for clarity of illustration. Relationships between elements in the drawings, such as top, bottom, left, right, top, bottom, etc., refer to how they appear and are located in the drawings. It should be understood that the terms and terminology used herein are not to be construed as limiting, but for descriptive purposes.

FIG. 1 is a diagram of a processing system according to an embodiment of the present invention. FIG. 2 is a partial perspective view of the plasma region of the processing system shown in FIG. 2A is a partial perspective view of the plasma region of the processing system shown in FIG. FIG. 3 is a partial perspective view of the pre-processing region, plasma region, and post-processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention. FIG. 2 is a diagram of elements of a processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention. FIG. 2 is a diagram of elements of a processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention. FIG. 2 is a diagram of elements of a processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention. FIG. 2 is a diagram of elements of a processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention. FIG. 2 is a diagram of elements of a processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention. FIG. 2 is a diagram of elements of a processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention. FIG. 2 is a diagram of elements of a processing region of the processing system of FIG. 1 in accordance with an embodiment of the present invention.

Detailed Description of the Invention

The present invention relates generally to the treatment of materials (such as surface treatments) to modify the properties of the material (such as cloth).

Various embodiments are described to illustrate the disclosure of the present invention, but are not intended to limit the present invention and are to be construed as illustrative. While the invention will be described in general in the context of various embodiments, it will be understood that it is not intended to limit the invention to these particular embodiments. Each embodiment is an example or implementation of one or more aspects of the invention. Although the various features of the invention may be described in the context of a single embodiment, these features may be provided separately or in any suitable combination with each other. Good. Conversely, although the invention may be described in the context of separate embodiments, the invention may be implemented as a single embodiment.

Hereinafter, the surface treatment of the base material, which is a dough supplied in a roll form (a long sheet of material wound around a cylindrical core) will be discussed. One or more treatments including but not limited to material synthesis may be applied to one or both surfaces of the dough substrate, and additional materials may be introduced. In this specification, a substrate is a thin sheet of material with two surfaces, the two surfaces being referred to as the front and back surfaces, or the top and bottom surfaces.

Some Embodiments of the Invention The following embodiments and aspects thereof are described and described in conjunction with systems, tools, and methods, which are illustrative and not limiting in scope. Specific configuration aspects and details are set forth to provide an understanding of the invention. However, it will be apparent to one skilled in the art that the present invention may be practiced without some of the specific details set forth herein. Furthermore, well-known features may be omitted or simplified in order not to obscure the description of the present invention.

FIG. 1 shows a method for performing processing such as the entire surface treatment system 100 and the surface treatment of the substrate 102. In the presented figure, the substrate 102 is shown as proceeding from right to left through the system 100.

The base material 102 is a dough material, for example, and is provided as a yarl as a long sheet on a roll. For example, the substrate to be treated is a fibrous fabric material such as cotton / polyster, which is about 1 meter wide, about 1 millimeter thick and about 100 meters long.

For example, a 1 mx 1 m area of substrate 102, which has not yet been processed, is shown as being unwound from supply reel R1 in input section 100A of system 100. From this input section 100A, the substrate 102 passes through the processing section 120 of the apparatus 100. After being processed, the substrate 102 exits the processing device 120 and is recovered in a suitable manner, such as winding on the take-up reel R2. For example, a 1 mx 1 m area of the substrate 102, the processed section 102B is illustrated as being wound on a take-up reel R1 in the output section 100A of the system 100. Various rollers R are provided between the various sections of the system 100 (shown) and in the sections (not shown) to guide the material through the system.

The processing unit 120 generally has three regions (zones or zones):
Any pre-treatment (ie precursor material) region 122,
A treatment (ie plasma) region 124,
Any post-processing (ie finishing) region 126

The processing region 124 includes components that generate a high voltage (HV) alternating current (AC) atmospheric pressure plasma (AP), these elements are well known, some of which are described in detail below. .

As a second energy source, a laser 130 is provided that provides a beam 132 that interacts with atmospheric pressure plasma in the main processing region 124 and strikes the surface of the substrate 102.

A controller 140 may be provided to control the operation of the various components and elements described above, and may include a conventional human interface (input, display, etc.).

FIG. 2 shows a portion of the main processing area 124 and some working elements. Three orthogonal axes x, y and z are shown (in FIG. 1, the corresponding x and y axes are shown).

Two elongated electrodes 212 (e1) and 214 (e2) are shown, and one is a cathode and the other is an anode. The two electrodes are arranged so as to be substantially parallel to each other and extend parallel to the y-axis, and are separated from each other in the x direction. For example, the electrodes e1, e2 are formed in any suitable manner, such as rods, tubes, and other rotatable cylindrical electrode materials, and nominally provide clearance for the thickness of the material being processed. They are separated from each other by a sufficient distance to allow. The electrodes e1 and e2 are arranged approximately 1 mm above the upper surface 102a of the substrate 102 to be treated.

The electrodes e1, e2 are energized in any suitable manner and surround the electrodes e1, e2 and between the electrodes e1, e2, called the plasma reaction zone, along the length of the resulting cathode / anode pair Atmospheric pressure plasma is generated in the immediate space.

As described above, the laser beam 132 is directed to the main processing region 124 and strikes the surface of the substrate 102. Here, the laser beam 132 is directed substantially along the y-axis, is shown substantially parallel to the electrodes e1, e2, between the electrodes e1, e2, and slightly above the upper surface 102a of the substrate 102. It interacts with the plasma (plum) generated by the two electrodes e1 and e2. In the illustrated application, the beam footprint is approximately 30 mm × 15 mm square. The beam may be directed vertically or horizontally to better obtain the desired interaction with the plasma and / or better obtain the desired direct substrate radiation.

The laser beam 132 is directed slightly but sufficiently off angle ("off angle") and is emitted directly to the substrate 102 to be processed while reacting simultaneously with the plasma generated between the two electrodes e1, e2. The More specifically, the laser beam 132 may form an angle “a” that is approximately 0 ° with respect to the top surface 102a of the substrate 102 so that it does not strike the top surface 102a of the substrate. Alternatively, the laser beam 132 may form an angle “a” that is less than about 1-10 ° with respect to the top surface 102a of the substrate 102 so as to strike the top surface 102a of the substrate. Other orientations of the beam 132 are possible and may be, for example, perpendicular (“a” = 90 °) to the top surface 102a of the substrate 102. The laser beam 132 is scanned using a conventional galvanometer or the like to interact with a selected portion of the plasma generated by the two electrodes e1, e2 or a selected portion of the substrate 102, or both. .

The plasma is generated using a first energy source such as high voltage (HV) alternating current (AC). A second separate energy source (such as a laser) interacts with the plasma, resulting in a hybrid plasma that interacts (in the processing region) with the substrate (material) being processed. It has become. In addition to interacting with the first energy source, the second energy source is also adapted to interact directly with the material being processed. Direct interaction with the substrate and other gases (secondary or pioneer) forms a plasma that is sustained by its own laser, which further interacts with and reacts with the plasma generated by the high voltage. Give higher energy to the environment.

The substrate 102 (the material being processed) is guided by a plurality of rollers as it passes through the main processing region (area) 124. FIG. 2A shows that one of these rollers 214 functions as the anode of the cathode / anode pair that generates the plasma and the other roller 212 functions as the cathode (the cathode and anode may be reversed). )It is shown that. In FIG. 2, the substrate 102 is disposed on one side (downward in the drawing) of both electrodes e1 and e2, and in FIG. 2A, the substrate 102 is disposed between the two electrodes e1 and e2. Please note that. In both cases, the plasma generated by the electrodes e1, e2 acts on at least one surface of the substrate 102. The anode and cathode may be coated with an insulating material such as ceramic.

It is understood that the present invention is not limited to any particular arrangement, i.e. the configuration of the electrodes e1, e2, and that the embodiment shown in FIGS. 2, 2A is intended only to illustrate some possibilities I want to be. Further, for example, instead of using two electrodes e1 and e2, a plasma jet train (not shown) for supplying plasma may be provided to form a desired plasma on the surface 102a of the substrate 102. Good.

FIG. 3 shows that in a pretreatment region 122, a spray head (nozzle) row 322 or other suitable means to cover the full width of the material to be treated is a solid, liquid or vapor phase precursor. It has been shown that the substance 323 can be discharged onto the substrate 102 to allow treatment of specific properties such as antibacterial properties, flame retardancy, superhydrophobicity, superhydrophilicity.

An intermediate buffer zone is provided between the pretreatment area (zone) 122 and the main treatment area (zone) 124 to allow time for the material applied in the pretreatment to soak (absorb) into the substrate. It may be. This process runs a single material length, but the buffer maintains, for example, up to 200 m of dough. For example, when a material being processed (such as a Yar) is being sent through the system at 20 meters / minute, this allows pretreatment (122) and hybrid plasma without stopping the material flow through the system. Several minutes of drying time will be allowed between treatments (124).

Similarly, in post-process area 126, a row of spray heads (nozzles) 326 or other suitable means to cover the full width of the processed (124) material is a solid, liquid or vapor phase finish. 327 may be discharged onto the substrate 102 to infiltrate the substrate with desirable characteristics.

Some Embodiments of Processing Region (124) FIGS. 4A-G illustrate various embodiments of elements in processing region.

FIG. 4A illustrates an embodiment.
Shows 400A,
The first (upper) roller 412 operates to function as the electrode e1, has a diameter of about 10 cm and a length of 2 meters (in-page direction). The roller 412 has a metal core and a ceramic (electrically insulating) outer surface.
The second (lower) roller 414 operates to function as the electrode e2, has a diameter of about 15 cm and a length of 2 meters (in-page direction). Roller 414 has a metal core and a ceramic (electrically insulating) outer surface.
The second roller 414 is parallel to the first roller 412 and disposed immediately below (in the drawing), and the gap (interval) between the first roller 412 and the second roller 414 is between the rollers 412 and 414. Corresponds to the thickness of the base material 402 (compared to 102) supplied to (for example, slightly smaller). The direction of material movement is from right to left as shown by the arrows. The base material 402 has an upper surface 402a (compared to 102a) and a lower surface 402b (compared to 102b).
The first roller 412 functions as the anode of the anode / cathode pair and is supplied with a high voltage (HV). The second roller 414 functions as the cathode of the anode / cathode pair and is grounded.
The first (right) nip roller or feed roller 416 (n1) is adjacent to the lower right (in the drawing) quadrant of the first roller 412 and the upper right (in the drawing) quadrant of the second roller 414. Adjacent to each other. Roller 416 has a diameter of about 12 cm and a length of 2 meters (in-page direction). The outer surface of the roller 416 is in contact with the outer surface of the roller 412. The gap between the outer surface of the roller 416 and the outer surface of the roller 414 corresponds to the thickness (a little smaller) of the substrate material 402 (compared to 102) supplied between the rollers 416, 414. ing.
The second (left) nip roller or feed roller 418 (n2) is adjacent to the lower left (in the drawing) quadrant of the first roller 412 and adjacent to the upper left (in the drawing) quadrant of the second roller 414 Are arranged. Roller 418 is approximately 12 cm in diameter and has a length of 2 meters (in-page direction). The outer surface of the roller 418 is in contact with the outer surface of the roller 412. The gap between the outer surface of the roller 418 and the outer surface of the roller 414 corresponds to the thickness (a little smaller) of the substrate material 402 (compared to 102) supplied between the rollers 418, 414. ing.
In general, the nip or feed rollers 416, 418 have an insulating outer surface to prevent a short circuit between the anode and the cathode 412, 414.

Such an arrangement of rollers 412, 414, 416, 418 defines a processing region 124 between the outer surfaces of the four rollers 412, 414, 416, 418 and contains a semi-air tight cavity (“440”) containing plasma. Form. The cavity 440 generally has a first (right) portion 440a of the space between the upper, right and lower rollers 412, 416, 414 and the first of the space between the upper, left and lower rollers 412, 418, 414. 2 (left side) portion 440b. A filled circle ● at the end of the lead wire of the right side portion 440a of the cavity 440 represents a gas flow into the cavity. A filled square (2) at the end of the lead wire of the left side portion 440b of the cavity 440 represents the laser beam (132).

The plasma generated in the cavity 440 is atmospheric pressure plasma (AP). Therefore, sealing of the cavity 440 is not necessary. However, end caps or plates (not shown) are disposed at the ends of the rollers 412, 414, 416, 418 to contain (partially confine) and control the gas flow in and out of the cavity 440.

FIG. 4B shows an embodiment 400B where the left and right rollers 416, 418 have moved slightly outward from the rollers 412, 414, allowing thicker and / or stiffer substrates to be processed. Thus, the cavity 440 is opened. However, this would require independent or direct driving of the anode and cathode electrodes. The material will be driven through the reaction zone by external feeding and slacking rollers.

FIG. 4C shows an embodiment 400C where a generally inverted U-shaped shield 420 is used instead of the left and right rollers (416, 418) to define a cavity 440 having left and right portions 440a, 440b. The shield 420 is disposed substantially completely around one roller 412 (except where the material is fed and passed) and is disposed at least partially around the other roller 414. . An additional shield (not shown) may be disposed below the lower roller 414.

FIG. 4D shows an embodiment 400D adapted for processing rigid substrates. The above-mentioned base material 402 was provided with flexibility like cloth. Rigid substrates such as glass for touch screen displays may be treated with hybrid plasma and precursors. A rigid substrate 404 having an upper surface 404a and a lower surface 404b passes between the upper roller (e1) 412 and the lower roller (e2) 414. A row of nozzles 422 (compared to 322) is arranged to provide a precursor, such as a liquid, solid, or atomized form. A shield (not shown) such as 420 referenced in FIG. 4C may be incorporated to contain the hybrid plasma.

FIG. 4E shows a configuration 400E that incorporates a row of HV plasma nozzles (jets) 430 rather than cylindrical electrodes e1, e2. For example, 10 jets 430 are provided in the processing region 124 at intervals of 20 cm. A rigid substrate 404 is shown. A row of nozzles 422 (compared to 322) is arranged to provide precursor material on the substrate 404, such as in an atomized form, in the pretreatment region 122 before the substrate is exposed to the hybrid plasma. For example, ten jets 422 are provided in the pretreatment region 122 at intervals of 20 cm. A shield (not shown) such as 420 referenced in FIG. 4C may be incorporated to contain the hybrid plasma. This configuration allows processing of metals or other conductive substrates.

FIG. 4F shows an embodiment 400D in which a first (upper) roller 412 that operates to function as electrode e1 (ie, anode) and a second (lower) that operates to function as electrode e2 (ie, cathode). ) Roller 414 and two nip rollers 436, 438 (compare 416, 418).

In contrast to embodiment 400A (FIG. 4A), in this embodiment, rollers 436, 438 are slightly outward (eg, 1 cm) away from upper and lower rollers 412, 414. Therefore, although it contains plasma, it will not function as a feed roller, and it will be necessary to provide a separate feed roller (not shown).

The right roller 436 (compare 416) is shown as having a layer or coating 437 on the surface. The right roller 436 (compared to 418) is shown as having a layer or coating 439 on the surface. For example, the rollers 436, 438 in the hybrid plasma processing region 124 are encased by a metal foil (or metal outer layer) and etched in the process by a high energy hybrid plasma and / or laser (second energy source). A plume containing a reactive metal plasma is formed, which immediately combines with the substrate surface radicals to form a nanolayer coating of the metal composition on the substrate material. The metal material (foil, layer) is controllably etched or ablated by the plasma, and the released metal component reacts with the plasma and is deposited on the substrate as a nanoscale layer or the like.

The metallic material coating of the rollers 436, 438 includes, for example, one or any combination of titanium, copper, aluminum, gold, silver. One roller may be coated with one material and the other roller may be coated with a separate material. Various different portions of the rollers 436, 438 may be coated with a variety of different materials. In general, when these materials are ablated, a vapor precursor is formed in the processing region 124 (and thus will be in contrast to the nozzles 322, 422 that provide the precursor in the preprocessing region 124).

FIG. 4G shows an embodiment 400G using plate electrodes 452, 454, which are two flat sheets rather than rollers (412, 414), and the two electrodes are spaced apart from each other in the processing region (reaction). / Synthetic zone) 124 through which the sheet of material 404 is fed. The gas supplied to the processing region is indicated by a circle 440a, and the laser beam is indicated by a square □ 440b. A nozzle 422 is provided to discharge the precursor in the pretreatment area 122. A nozzle 426 is provided for discharging the finishing material in the post-processing area 126.

Additional features Although not specifically indicated, the finish material provided on the substrate 102 after the hybrid energy treatment (124) is exposed to an adjacent secondary or hybrid plasma, Subsequent to activation of the surface by hybrid plasma, the supplied finishing material may be dried, sealed and reacted.

Although not specifically shown, various gases such as oxygen, nitrogen, hydrogen, carbon dioxide, argon, helium, or silane or siloxane are used to impart various desirable characteristics and properties to the treated substrate. A compound such as a material may be introduced into the plasma, for example, within the processing region 124.

Introducing precursors such as non-silver based silanes / siloxanes and aluminum chloride families such as 3 (trihydroxylsilyl) propyldimethyl octadecyl ammonium chloride in order to impart bactericidal properties to the material being treated. May be. Similar to siloxane and ethoxysilane (which improves hydrophobicity) other silane / siloxane groups may be used to affect hydrophobicity. Applying hexaethyldiosilane in the gas phase of the plasma smoothes the surface of the textile fiber and increases the contact angle, which is an indicator of the level of hydrophobicity.

A negative draft, i.e., an atmospheric partial vacuum, may be employed to draw the plasma composition component and further penetrate the thickness of the porous substrate. FIG. 3 shows a suction means, such as a platen (bed) 324, over which the substrate 102 passes in the processing region 124, and the suction means includes a plurality of holes to produce the desired effect. And connected to suction means (not shown) in an appropriate manner. The platen 324 may function as one of the electrodes that generate plasma. Alternatively, this function may be implemented by appropriately deforming a roller or the like (provided with a hole and connected to a suction means).

The process is dry, has a low environmental impact, residual or by-product gases and components are inherently safe, exhausted from the system, and recycled or disposed of in an appropriate manner. Please understand that.

A method of processing a material using at least two energy sources is provided, the two energy sources comprising: (i) an atmospheric pressure plasma generated by various gases passing through a high energy electromagnetic field; and (ii) the plasma. And at least one laser that interacts and generates a hybrid plasma. The laser operates in the ultraviolet wavelength range such as 308 nm or less. Lasers include excimer lasers that operate at an output power of at least 25 watts, including greater than 100 watts, greater than 150 watts, greater than 200 watts. The laser may be a pulse with a frequency of 25 Hz or higher, such as 350-400 Hz, and includes a picosecond or femtosecond laser. Although one laser has been described as interacting with the plasma (and the substrate), it is within the scope of the invention to use more than one laser.

Some exemplary parameters for generating a plasma in the processing region are: a gas mixture of 80% argon, 20% carbon dioxide with oxygen, 1-2 Kw (kilowatts) for HV generated plasma, and 500 mjoules for a 308 nm UV laser. 350Hz.

Instead of or in addition to using a laser, an ultraviolet (UV) source, such as an ultraviolet lamp or an array of high power UVLEDs (light emitting diodes), placed along the length of the treatment area, can be used to generate atmospheric pressure plasma. Energy may be directed to generate a hybrid plasma and to interact with the material being processed (etching, reaction, synthesis, etc. on the material).

Primarily, the above describes the treatment of one surface 102a of the substrate 102 and describes some exemplary treatments. It is within the scope of the present invention to process the opposite lower surface 102b of the material 102, such as by looping back the material 102 and passing it through the processing chamber 124. Various energy sources and environments, precursor materials and finishing materials may be used to treat the second surface of the material. In this way, both sides of the material are processed. It will also be appreciated that processing may affect the interior of the surface of the material being processed to alter or increase the properties of the internal (core) material. In some cases, the top and bottom surfaces of the material and the core are effectively treated from one side.

The system can be used to process materials other than sheet format. For example, the present invention can be used to improve the optical and morphological characteristics of organic light emitting diodes (OLEDs) by hybrid energy annealing. Such individual materials are conveyed (conveyed) through the system in some suitable manner.

Other types of energy may be combined or applied sequentially to each other to produce increased throughput. For example, methods of processing materials include microwaves and lasers, microwaves and electromagnetically generated plasma, plasmas and microwaves, or plasma, laser, and pulsed microwave electron cycloton resonance (ECR). It uses a combination of at least two energy sources, such as various combinations.

The two energy sources are (i) an atmospheric pressure plasma using various ionized gases that pass through a high energy electromagnetic field, and an ultraviolet (UV) source that produces radiation and directs the highly ionized plasma and the surface to be treated directly. It is equipped with. The UV source includes an array of high power UVLEDs (light emitting diodes) arranged along the extent of the processing area. The high-power ultraviolet LED interacts with the plasma to give the plasma high energy, and directly acts on the substrate to etch or react with the substrate.

An automated material delivery system may controllably deliver material through an energy field generated by a combined energy source.

A series of processing steps are performed as follows:
Step 1-(Optional) precursor application,
Step 2-Exposure to hybrid energy,
Step 3-(Optional) Precursor or finishing material application,
Step 4-Exposure to hybrid energy,
All steps are accomplished in a continuous manner within the system.

It is within the scope of the present invention to introduce a delivery system that can add a gas / vapor phase precursor directly to the plasma reaction zone for this process.

Some typical process parameters
Treatment 1 Hydrophilic precursor Polydimethylsiloxane Hydroxycut (PMDSO Hydroxycut)
Alternative: Copolymer (blend of dimethylsiloxane and / or dimethylsilane)
Laser frequency 250Hz
Power 380mJ
Plasma carrier gas Argon… 80%
Reaction gas Oxygen… 20%
Flow rate 15liter / min Pressure: Slightly higher than 1bar Power 2KW

Process 2 dyeable precursors Lasers without precursors and other precursor catalysts Frequency 250Hz
Power 380mJ
Plasma carrier gas Argon… 80%
Reaction gas Oxygen or nitrogen… 20%
Flow rate 15liter / min Pressure: slightly higher than 1bar Power 2KW

Treatment 3 Hydrophobic precursor octamethylcyclotetrasiloxane / polydimethylsilane blend (water soluble), hydrogen methyl polysiloxane mixed with dimethylpolysiloxane with polyglycol ether (water soluble), or the above and dimethylpoly A combination of siloxanes. Using a water soluble blend allows the material to be diluted with deionized water to the required concentration based on application, cost effectiveness, and output performance results. Water soluble blends are produced using suitable additives. These are essentially methods in which oil is mixed with water to produce an emulsion, generally the size of an emulsion dispersant, i.e. macro or micro (macro> 100 microns, micro <30 microns). is there.
Alternative: Copolymer (blend of dimethylsiloxane and / or dimethylsilane)
Laser frequency at least 350Hz
Power at least 450mJ
Plasma carrier gas Nitrogen, argon, helium… 80%
Reaction gas Carbon dioxide or nitrogen… 2-20%
Flow rate 10-40liter / min Pressure: slightly higher than 1bar Power 0.5-1KW

Treatment 4 Flame Retardant Performance Polysilanes and terpolymers based on precursor silane / siloxane and polyborosiloxane with transition oxides of major inorganic compounds, essentially titanium, silicon, zirconium, boron. Also included are boron containing siloxane copolymers and terpolymers, such as organosilicon / oxyethyl modified polyborosiloxanes. Depending on the type of substrate material and output requirements, several limited material compositions based on recent new phosphorous acid blends may be used. Octamethylcyclotetrasiloxane / polydimethylsilane blend (water soluble) mixed with polydimethylsiloxane with polyglycol ether (water soluble) or a combination of the above and polydimethylsiloxane with the following additives.
-Calcium metaborate added to silane / siloxane-Silicon oxide added to silane / siloxane-Titanium isopropoxide additive-Titanium dioxide (rutile)
-Ammonium phosphate-Aluminum oxide-Zinc borate-Boron phosphate containing preceramic oligomers-Aerogels and hydrogels, low or high density cross-linked polyacrylates-Nano / micro encapsulated compositions Example: Dimethylsiloxane, and / Or dimethylsilane with polyborosiloxane, with addition of transition oxide in the capacity range of 5-10% of oxides such as titanium dioxide, silicon dioxide (fumed, gel or amorphous), aluminum oxide etc. Yes.
The precursors described herein increase the flame retardancy of the materials in the systems described herein by using a hybrid plasma (eg, using a laser). It is within the scope of the present invention for the precursors described herein to increase the flame retardance (or other properties) of materials in material processing systems by using non-hybrid plasmas (eg, without the use of a laser). It is.
laser
Frequency at least 350Hz
Power at least 450mJ
Plasma carrier gas Nitrogen, argon, helium… 80%
Reaction gas Carbon dioxide or nitrogen… 2-20%
Flow rate 10-20liter / min Pressure: Slightly higher than 1bar Power 0.5-1KW

Treatment 5 Silane / siloxane blend as hydrophobic platform with addition of antimicrobial precursor dimethyloctadecyl (3triethoxylpropyl) ammonium chloride.
Octamethylcyclotetrasiloxane / polydimethylsilane blend (water soluble) mixed with polydimethylsiloxane with polyglycol ether (water soluble) or a combination of the above and polydimethylsiloxane with the following additives.
-Dimethyloctadecyl (3 trimethoxysilylpropyl) ammonium chloride-chitosan laser
Frequency at least 350Hz
Power at least 450mJ
Plasma carrier gas Nitrogen, argon, helium… 80%
Reaction gas Carbon dioxide or nitrogen… 2-20%
Flow rate 10-20liter / min
Pressure: slightly higher than 1bar Power 0.5-1KW

Although the invention has been described in connection with a limited number of embodiments, they should not be construed as limiting the scope of the invention, but as an example of some embodiments. Those skilled in the art will envision other possible variations, modifications, and implementations, which are considered to be within the scope of the present invention and are claimed based on the disclosure herein. Also good.

Claims (31)

A method for treating a substrate (102, 402, 404),
Generating a plasma in a processing region (124) comprising two spaced apart electrodes (e1 / e2; 212/214; 412/414; 452/454);
Directing at least one second energy source different from the first energy source to the plasma to interact with the plasma to obtain a hybrid plasma;
Interacting the hybrid plasma with a substrate in the treatment region (124);
Method. The first energy source comprises a high voltage alternating current (AC);
The second energy source comprises radiation from a laser;
The method of claim 1. The laser interacts with the plasma and directly affects the material being processed;
The method of claim 2. The laser has at least one of the following features:
The laser comprises an excimer laser;
The laser operates in the ultraviolet (UV) wavelength range;
The laser operates at an output power of at least 25 watts;
The method according to claim 2.   The method of claim 2, wherein the plasma comprises atmospheric pressure plasma (AP).   The method according to any one of the preceding claims, wherein a precursor (323,437) is fed (122,322,422) onto the substrate prior to treating the substrate.   The method of any one of the preceding claims, wherein after treating the substrate, a finishing material (327,439) is fed (126,326,426) onto the substrate.   The method of claim 1, wherein the plasma comprises a high voltage (HV) atmospheric pressure (AP) plasma.   The method according to claim 1, wherein the electrodes (e1 / e2) are rollers (212/214; 412/414).   The method according to claim 1, wherein the substrate is a material.   The method according to claim 1, wherein the substrate is a synthetic fabric material.   The method of claim 11, wherein the synthetic fabric material is polyester. The method according to claim 1, wherein the substrate is an organic material.   The method of claim 13, wherein the organic material comprises at least one selected from cotton and wool. Equipment for processing materials (100, 400A, 400B, 400C, 400D, 400E, 400F, 400G),
Two spaced electrodes (e1 / e2; 212/214; 412/414) that generate plasma in the processing region (124);
One or more lasers (130) that direct one or more corresponding beams (132) to the processing region and interact with at least one of the plasma and the material being processed;
With a device. The two spaced apart electrodes (e1 / e2) are a first roller and a second roller (412/414),
Further, a third roller and a fourth roller (416/418) are disposed in proximity to the first roller and the second roller, and the first roller, the second roller, the third roller, and the fourth roller (412, 414, 416, 418). 16. An apparatus according to claim 15, wherein a processing region (124) is defined between the outer surfaces of the substrate and a semi-air tight cavity (440) containing a plasma is formed (FIGS. 4A, 4B, 4F). The third roller and the fourth roller (436,
The apparatus of claim 16, wherein at least one of 438) comprises a metal outer layer (437, 439) (FIG. 4F). The two spaced apart electrodes (e1 / e2) are a first roller and a second roller (412/414),
Furthermore, it is arrange | positioned so that the said 1st roller and 2nd roller (412,414) may be enclosed, and the shield (420) which defines a cavity (440) is provided (FIG. 4C), It is any one of Claims 15-17 apparatus. Nozzles (322, 422) and (Figures 4D, 4E) that discharge precursors in liquid, solid or atomized form,
A nozzle (326) that discharges the finishing material (327) to the material being processed (Figure 3),
The apparatus according to claim 15, comprising at least one of the following:   20. Apparatus according to any one of claims 15 to 19, wherein the two spaced apart electrodes (e / e2) are a first plate and a second plate (452, 454) (Fig. 4G).   21. Use of an apparatus according to any one of claims 15 to 20 for treating a dough substrate.   The use according to claim 21, wherein the dough substrate is a synthetic dough material.   23. Use according to claim 22, wherein the synthetic fabric material is polyester.   The use according to claim 21, wherein the substrate is an organic material.   The use according to claim 24, wherein the organic material is at least one selected from cotton and wool.   The dough material obtained by the method of any one of Claims 1-14. A method for generating plasma for material processing, comprising:
Combining at least two energy sources selected from high voltage, plasma, laser, ultraviolet lamp, pulseable microwave electron cycloton resonance (ECR),
Method.   28. The method of claim 27, wherein one of the at least two different energy sources is one that generates an atmospheric pressure plasma (AP). One energy source is plasma,
The other energy source is a laser beam directed to the plasma,
28. The method of claim 27.   29. A method according to any one of claims 27 and 28, wherein the laser beam is directed to the material being processed.   31. A method according to any one of claims 27 to 30, wherein the plasma is provided by a plasma nozzle.

Images