ES2680653T3 - Method and apparatus for surface treatment of materials using various combined energy sources - Google Patents

Abstract

A method for the treatment of a substrate (102,402,404) consisting of: A high voltage (HV) of alternating current (AC) and atmospheric pressure (AP) is created for the treatment of the plasma in the area (124) that comprises two electrodes separated from each other (e1/e2;212/214;412/414) where the electrodes are provided with the first and second rollers (212/214;412/414) located parallel to each other, with a gap between them, the gap corresponds to the thickness of the substrate, which allows the substrate to be fed from the rollers, characterized in that the method consisting of: At least one laser beam (132) is directed into the treatment area, approximately parallel between the electrodes and slightly above the top of the substrate surface (102a), which interacts with the plasma, creating a hybrid plasma; wherein at least one laser beam is directed at an angle (α) of less than 1-10 degrees where the top of the substrate is being treated to be directly irradiated and coincidentally reacts with the plasma being generated by the two electrodes; and creating a hybrid plasma that interacts with the substrate in the treated area (124).

Description

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Method and apparatus for surface treatment of materials using various combined energy sources

TECHNICAL SCOPE

The invention refers to the surface treatment of materials and various substrates, specifically, and, for example, textiles and, specifically, to the treatment of materials with a combination of several different energy sources, among which one is normally atmospheric plasma.

BACKGROUND

The development of "smart textiles" has long been an area of study to improve various properties, such as stain resistance, impermeability, color fixation and other characteristics that can be achieved through advanced treatment with plasma technologies , microwave energy sources and, in some cases, chemical treatments.

Atmospheric plasma treatment (APT) improves fiber surface properties, such as hydrophilicity, without affecting their internal properties, and can be used by textile manufacturers and processors to improve the surface properties of natural and synthetic fibers in order to increase adhesion, wettability, stamping capacity and tinting and to reduce shrinkage of the material.

Atmospheric pressure plasma (also known as AP plasma or normal pressure plasma) is the special case of plasma in which the pressure approximately corresponds to the surrounding atmospheric pressure. AP plasmas are of great technical importance, since, unlike low-pressure plasmas or high-pressure plasmas, it is not necessary to use any expensive reaction vessel that guarantees the maintenance of a pressure level other than atmospheric pressure. In addition, in many cases, these AP plasmas can easily be incorporated into the production line. Various forms of plasma excitation are possible, including AC excitation (alternating current), DC excitation (direct current) at low frequency, radio wave excitation and microwave excitation. However, only AP plasmas excited by CA have reached a remarkable industrial relevance.

In general, AP plasmas are generated by CA excitation (corona discharge) and plasma jets. A pulsed electric arc is generated in the plasma jet by means of a high voltage discharge (5-15 kV, 10-100 kHz). A process gas, such as compressed air without oil, flows through this discharge section, becoming excited and becoming plasma. This plasma then passes through an injector head until it reaches the surface of the material to be treated. The injector head has a ground potential and, thus, largely retains particles in the plasma flow with potential. In addition, the injector head determines the geometric shape of the emerging jet. Several injector heads can be used for the corresponding area of the substrate being treated. For example, the materials arranged in sheets, sheets or fabrics with several meters of width to be treated can be treated by a row of injectors.

AP plasma and vacuum plasma have long been used to clean and activate material surfaces to prepare them for adhesion, stamping, painting, polymerization or other functional or decorative coatings. AP plasma processing may be preferable to vacuum plasma for continuous material processing. Another method of surface treatment uses microwave energy to polymerize precursor coatings.

The German patent application open for public inspection DE 36 19 694 A1 describes a method and an apparatus for creating clusters of functional atoms on the surface of macromolecular substrates, such as cellulose or wool, in which the substrate is subjected to a discharge Silent electrical before or simultaneously to irradiation with ultraviolet light. Ultraviolet light bulbs point perpendicular to the substrate to be treated.

JP 61119676 describes the generation of a thin film on a substrate after treatment thereof in a vacuum treatment chamber and its heating at a certain temperature. A plasma film is formed some distance from the substrate. Next, a laser beam is directed towards the substrate perpendicular to the plasma film.

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In US patent document 2008/0055594 A1 a hybrid element analyzer by plasma is described. Plasma is generated between a ground electrode and a high voltage electrode. Both electrodes form an annular region into which the sample is introduced. Microwave radiation is coupled to the plasma to maintain it.

Hammen et al. (US 2009/0120782 A1) describe a discharge surface treatment apparatus with continuous feeding to treat mesh materials. This apparatus incorporates a discharge chamber in which the ionization of a process gas takes place through the application of high voltage.

SUMMARY

The invention is defined in the claims.

The invention is generally intended to offer improved techniques for treating (such as treating and modifying surfaces) materials, such as substrates, and more specifically, textiles (including knitted or knitted textiles and non-woven fabrics). knitting), and in broad strokes it requires the combination of different additional energy sources (such as laser irradiation) with one or several high voltage generated plasmas (such as atmospheric pressure plasmas [AP]) to carry out the treatments, which can alter the interior of the treated material, in addition to the surface, and that may use introduced gases or precursor materials in a dry environment. Combinations of different energy sources are described herein.

An embodiment of the invention broadly comprises a method and an apparatus for treating and making technical textiles and other materials using a combination of at least two energy sources that interact with each other, such as lasers and atmospheric plasma (AP) generated at high voltage.

The techniques described herein can easily be incorporated into a system for the automatic processing of textile materials. Functionality can be achieved by cleaning without aqueous solutions, such as etching or ablation, by activating the formation of radicals on the surface or surfaces and increasing and reducing, simultaneously and selectively, the desired functional properties. The various properties, such as hydrophobicity, hydrophilicity flame retardant properties, antimicrobial properties, shrinkage resistance, fiber abrasion, hydrophobic properties, dyeing at low temperatures, increased dye absorption and color fixation, can achieved or improved, increased or reduced, by means of one or more processes that cause chemical or morphological changes, such as the formation of radicals on the surface of the material. Material coatings, such as nanometric scale coatings in the composition of advanced materials, can also be applied and processed.

The combination (or hybridization) of the energy of the AP plasma with a laser beam as a secondary energy source may result in a more efficient (and commercially viable) energy environment for substrate treatment. The secondary energy source can be applied in combination (jointly or simultaneously) or sequentially (successively or selectively) with the energy of the AP plasma to achieve the desired properties.

The secondary energy source can act on the plasma column generated separately, so that a more efficient and more energy plasma environment is obtained, at the same time as the possibility of acting directly on the surface is available and, in some cases , the interior of the material subject to this hybrid treatment.

The techniques described herein can be applied, although not exclusively, to the treatment of textiles (both organic and inorganic), paper, synthetic paper, plastic and other similar materials that normally take the form of a sheet, sheet or roll fabric ("articles of sale by meters »). The techniques described herein can also be applied to the extrusion of plastics or metals, laminators, injection molding, spinning, carding, weaving, glass fabrication, substrate etching and cleaning and the coating of any material, as well as almost any material processing technique. By means of the described techniques, rigid materials can be treated, such as glass sheets (for example, those used in touch screens).

In accordance with one aspect of the present invention, a method for treating a substrate, as defined in claim 1, is set forth.

In another aspect, the present invention includes an apparatus, as defined in claim 7.

In a further aspect, the present invention comprises a use of the apparatus described herein for the treatment of a textile substrate.

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In a different aspect, the present invention conceives a textile material obtained with the method described herein.

The advantages of the present invention may include, among others, a method for creating a plasma with greater energy and more efficient for cleaning and activating surfaces for further processing or finishing. For example, ultraviolet laser irradiation, both continuous and pulsed, can be combined with AP plasma generated by electromagnetic means to create a strongly ionized and more energy reactive environment for surface treatment. The effect of the resulting hybrid energy may be greater than that of the sum of its various components. Pulsed laser energy can be used to conduct the plasma, so that waves are generated and the laser energy accelerates the resulting plasma waves, which act on the substrate in a manner similar to the action of waves in the sea.

This accelerated and higher energy plasma can give rise to radicals in the fiber or surface of the treated substrate and fix ionized groups to said radicals. Said functional groups, such as carboxyl, hydroxyl or others, are fixed to the surface improving the polarity characteristics and can lead to greater hydrophilicity and other desirable functional properties.

The invention conveniently combines energy sources in a controlled atmospheric environment in the presence of a material substrate. The end result can be the conversion and synthesis of materials on the surface of the substrate: the substrate can undergo a physical alteration, in contrast to a simple coating.

In an exemplary embodiment, a high frequency radiofrequency plasma is created in a compartment (or cavity, or chamber) formed between rotating and driven rollers and extending over the entire width of the processing area . The plasma field generated is uniform throughout the width of the treatment area and can act at atmospheric pressure. It also includes a high power ultraviolet laser to interact with the plasma or the material in question. It is possible to modify the shape of the laser beam so that it has a rectangular cross-section and a uniform energy density throughout the entire treatment area. A gas supply system can be used to combine any amount of environmental gases and precursors (for example, four) into a single feed gas that fills the hybrid plasma chamber. A spray or nebulizer system capable of applying a thin and uniform layer of sol-gel material or process accelerators can also be incorporated into the material to be treated, before or after processing.

The process of combining plasma and photonics (such as ultraviolet lasers) is dry, is carried out at atmospheric pressures and uses safe and inert gases (such as nitrogen, oxygen, argon and carbon dioxide). By changing the power of the laser and plasma and by varying the ambient gases or by adding sol-gel materials or other organic or inorganic precursors - that is, by changing the "recipe" - the system offers a wide variety of process applications .

Some of these applications are cleaning, preparation and improvement of material performance.

- In cleaning, the laser can intensify plasma power and act on the substrate material itself.

- In the preparation of the substrate material for secondary processing, such as dyeing, the ablation of the fiber surface can be performed in a controlled manner, thereby increasing the hydrophilicity of the material (for example, in textile materials). In addition, by introducing environmental gases into the system's processing zone, chemical substances can be created on the surface of the material (e.g., a cloth), which can react with the dyeing media to achieve more effective dye penetration, a more intense coloring process or a reduction in staining temperature. For example, textile fibers can be prepared to achieve a more controlled absorption of chromium oxide dyes and thus increase the intensity of the black color obtained. Therefore, there is potential in this process to reduce the chemical content of the dyes, which could reduce both the negative environmental impact and the processing costs.

- In relation to performance improvement, through the process the synthesis of materials on the surface of the substrate can be achieved. By altering the powers and frequencies of the laser and plasma, and thanks to the introduction of other materials in the process environment, the system achieves ablation of the substrate surface and, through various chemical reactions between the substrate and the environmental gases, new materials are synthesized on the surface of the fibers of the mesh of the textile material.

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Reference may be made in detail to embodiments of the described invention, in relation to which some non-exhaustive examples may be illustrated in the accompanying drawings (or figures, or FIGS). In general, the figures are schematic drawings. To offer greater clarity, some elements of the figures can be exaggerated and others omitted. Reference can be made to the relationship or to the relationships between the different elements of the figures depending on the way in which they are presented or placed in the drawings, such as, for example, "up", "down", "left", "right" , "Above", "below" or similar terms. The wording and terminology used herein should not be construed restrictively and should be considered as being used for descriptive purposes only.

FIG. 1 is a schematic representation of a treatment system according to an embodiment of the invention.

FIG. 2 shows a partial perspective view of a plasma area of the treatment system illustrated in FIG. 1. It is not part of the invention.

FIG. 2A shows a partial perspective view of a plasma area of the treatment system illustrated in FIG. one.

FIG. 3 shows a partial perspective view of a pretreatment area, a plasma area and a post-treatment area of the treatment system illustrated in FIG. 1 according to some embodiments of the invention.

FIGS. 4A to 4F are schematic representations of elements of a treatment area of the treatment system illustrated in FIG. 1 according to some embodiments of the invention.

DETAILED DESCRIPTION

The invention generally refers to the treatment (such as, for example, surface treatment) of materials (for example, textiles) to modify their properties.

Various embodiments will be described to illustrate the invention or the inventions and such embodiments should be considered illustrative and not exhaustive. Although the invention is generally described in the context of several examples of embodiments, it should be understood that with said description it is not intended to limit the invention to these specific embodiments. Each embodiment may constitute an example or implementation of one or more aspects of the invention or the inventions. Although various features of the invention or inventions can be described in the context of each embodiment, the features can also be stated separately or in any combination with each other that is suitable. On the other hand, although the invention or the inventions can be described in the context of different embodiments, said invention or said inventions can also be practiced following a single embodiment.

In the main description that follows, we will talk about the surface treatment of substrates, which can be textiles supplied in rolls (long sheets of material or fabrics rolled in a coil). One or more treatments, including, among others, the synthesis of materials, can be applied to one or both sides of the textile substrate and additional materials can be introduced. For the purposes of the present, "substrate" means a thin "sheet" of material or fabric with two faces, which can be referred to as "front" and "back" or "top" and "bottom" faces.

SOME EMBODIMENTS OF THE INVENTION

The following embodiments and the following aspects of these can be described and illustrated together with systems, tools and methods set forth by way of illustrative example, which in no case should be considered exhaustive. Concrete designs may be indicated to provide a detailed view of the invention or inventions. However, it should be apparent to those skilled in the art that it may be possible to implement the invention or inventions without some of the specific details presented in this document. In addition, some known features may be omitted or simplified so as not to complicate the descriptions of the invention or the inventions.

FIG. 1 shows a complete surface treatment system (100) and a method for performing the treatment, such as, for example, the surface treatment of a substrate (102). In the figures presented, the substrate (102) is shown advancing through the system (100) from right to left.

The substrate (102) can be, for example, a textile material and can be supplied, in the manner of "sale items per meter", as a fabric wound in a reel. The substrate to be treated may be, for example, a fibrous textile material, such as cotton / polyester, approximately 1 m wide, approximately 1 mm thick and approximately 100 meters long.

5 A part of the material (102A), such as a part of the substrate (102) of 1 x 1 m still untreated, is illustrated leaving a feed roll (R1) in a feed section (100A) of the system (100). From the feed section (100A), the substrate (102) passes through a treatment section (120) of the apparatus (100). After treatment, the substrate (102) leaves the treatment apparatus (120) and can be collected in any way that is suitable, such as, for example, rolled up in an exit roll (R2). A part of the material (102B), such as a part of the substrate (102) of 1 x 1 m already treated, is illustrated by winding in an exit roll (R2) in an exit section (100B) of the system (100) Several rollers (R) can be included between the different sections of the system (100) (as shown) and within the different sections (not shown) to guide the material through the system.

The treatment section (120) can generally comprise three areas (or regions, or zones):

- optionally, a pretreatment area (or precursor) (122);

15 - a treatment area (or plasma) (124);

- optionally, a post-treatment (or finishing) area (126).

The treatment area (124) incorporates components to generate atmospheric plasma (AP) with alternating current (AC) at high voltage. Its elements are generally known and some of them are described in more detail below.

A laser (130) is included as a secondary energy source to create a beam (132) that interacts with the AP plasma in the main treatment area (124) and also affects the surface of the substrate (102).

A controller (140) can be incorporated to control the operation of the various components and elements described previously and can be provided with the usual user interfaces (command input system, display, etc.).

25 The configuration shown in FIG. 2 is not part of the invention, but serves to illustrate it. FIG. 2 shows part of the main treatment area (124) and some operational elements of it. Three orthogonal axes (x, y and z) are included. (In FIG. 1, the corresponding x and y axes are included.)

Two elongated electrodes (212 [e1] and 214 [e2]) are shown, one of which can be considered a cathode and the other an anode. These two electrodes (e1 and e2) can generally be arranged parallel to each other, parallel to the y-axis 30 separated from each other in the direction of the x-axis. The electrodes (e1 and e2) may have any form that is suitable, such as a rod, tube or any other type of rotating cylindrical electrode, and, in principle, they are separated from each other at a distance that leaves sufficient space for the thickness of the processed material. The electrodes (e1 and e2) can be arranged approximately 1 mm above the upper face (102a) of the substrate (102) to be treated.

The electrodes (e1 and e2) can be energized in any way that is suitable for creating atmospheric plasma (AP) along the cathode and anode pair in the space between the electrodes (e1 and e2) and directly around them, which we can refer to as "plasma reaction zone".

As previously mentioned, a laser beam (132) can be directed to the main treatment area (124) and said beam can also affect the surface of the substrate (102). In FIG. 2, the laser beam (132) directed 40 is shown approximately along the axis and, approximately parallel to the electrodes (e1 and e2) and between them, and slightly above the upper face (102a) of the substrate ( 102), so that it interacts with the plasma (column) generated by both electrodes (e1 and e2). In an example of application, the area of incidence of the beam can be a rectangle of approximately 30 x 15 mm. The beam can be oriented vertically or horizontally to facilitate the desired plasma interaction or direct irradiation of the substrate.

The laser beam (132) is directed lightly but sufficiently "deflected" to directly irradiate the substrate (102) that must be treated while reacting at the same time with the plasma generated by the two electrodes (e1 and e2). Specifically, the laser beam (132) deviates with an angle "a", which is approximately less than 1-10 degrees relative to the face

upper (102a) of the substrate (102) so that it affects said upper face (102a). The laser beam (132) can be inspected by means of conventional galvanometers or some similar instrument, so that it interacts properly with any selected part of the plasma generated by the two electrodes (e1 and e2), with the substrate (102) or with both.

5 Plasma is created using a first source of energy, such as high voltage alternating current (AC). A second different energy source (such as the laser) interacts with the plasma, generating a «hybrid plasma», and said hybrid plasma interacts (in the treatment area) with the substrate (the material) to be treated. In addition to interacting with the first source of energy, the second source of energy must also interact directly with the material to be treated. Direct interaction with the substrate or other gas (secondary or precursor) can generate its own laser-maintained plasma, which, in turn, can interact with the plasma generated by high voltage to increase the energy of the reactive environment.

The substrate (102) (material in question) is guided by rollers as it crosses the main treatment area (zone) (124). FIG. 2A shows that one of these rollers (214) functions as the anode and the other (212), as the cathode (or vice versa) of an anode and cathode pair arranged to generate the plasma. It should be noted that, in FIG. 2, the substrate (102) is located on one side of both electrodes (e1 and e2) (below these, in the illustration), and, in FIG. 2A, the substrate (102) is disposed between the two electrodes (e1 and e2). In both cases, the plasma generated by the electrodes (e1 and e2) acts, at least, on one of the faces of the substrate (102). The anodes and cathodes may be coated with an insulating material, such as a ceramic material.

FIG. 3 shows that, in the pretreatment area (zone) (122), a row of spray heads (nozzles) 20 (322) covering the entire width of the material to be treated, or any other suitable means may be used, to dispense precursor materials (323) in solid, liquid or gaseous phase in the substrate (102) and thus allow the processing of certain properties, such as antimicrobial, flame retardant or superhydrophobic / hydrophilic characteristics.

There may be an intermediate separation zone between the pretreatment area (zone) (122) and the area (zone) of the main treatment (124) in order to allow time for the materials applied in the pretreatment phase to be infused in the substrate (be absorbed by it). The system will continue to process a continuous material, but the separation zone can retain, for example, up to 200 m of fabric. When the material to be treated (such as, for example, sale items per meter) enters, for example, in the system at 20 m / min, this separation zone allows a "drying time" of several minutes between pretreatment (122) and hybrid plasma treatment (124) without interrupting the flow of material through the system.

Similarly, in the post-treatment area (zone) (126), a row of spray heads (nozzles) (326) covering the entire width of the material to be treated (124), or any other means can be used suitable, to dispense the finishing materials (327) in solid, liquid or gaseous phase in the substrate (102) and thus confer on it the desired characteristics.

35 Some embodiments of the treatment area (124)

FIGS. 4A to 4F illustrate various embodiments of elements of the treatment area (124).

FIG. 4A illustrates an embodiment (400A) with the following characteristics:

- A first ("upper") roller (412) functions as an electrode (e1) and can have a diameter of approximately 10 cm and a length (perpendicular to the illustration) of 2 m. This roller (412) can

40 incorporate a metal core and a ceramic outer surface (electrical insulator).

- A second roller ("lower") (414) functions as an electrode (e2) and can have a diameter of,

approximately 15 cm, and a length (perpendicular to the illustration) of 2 m. This roller (414) can incorporate a metal core and a ceramic outer surface (electrical insulator).

- The second roller (414) is arranged parallel to the first roller (412) and directly below

45 east (as shown in the illustration), with a separation space that corresponds to the thickness

(for example, it may be slightly less than the thickness) of the substrate material (402) (equal to 102) that is passed between both rollers (412 and 414). The material can move from right to left, as indicated by the arrow. The substrate (402) has an upper face (402a) (equal to 102a) and a lower face (402b) (equal to 102b).

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- The first roller (412) can serve as an anode of a pair of anode and cathode and can receive high tension. The second roller (414) can serve as a cathode of the anode and cathode pair and can be grounded.

- A first presser or feed roller ("right") (416) (n1) is adjacent to the lower right quadrant (according to the illustration) of the first roller (412) and the upper right quadrant (according to the illustration) of the second roller (414). This roller (416) can have a diameter of approximately 12 cm, and a length (perpendicular to the illustration) of 2 m. The outer surface of this roller (416) may be in contact with the outer surface of the first roller (412). The space between the outer surface of this roller (416) and the outer surface of the second roller (414) corresponds to the thickness (for example, it may be slightly less than the thickness) of the substrate material (402) (equate to 102) which is passed between both rollers (416 and 414).

- A second presser or feed roller ("left") (418) (n2) is adjacent to the lower left quadrant (according to the illustration) of the first roller (412) and the upper left quadrant (according to the illustration) of the second roller (414). This roller (418) can have a diameter of approximately 12 cm, and a length (perpendicular to the illustration) of 2 m. The outer surface of this roller (418) may be in contact with the outer surface of the first roller (412). The space between the outer surface of this roller (418) and the outer surface of the second roller (414) corresponds to the thickness (for example, it may be slightly less than the thickness) of the substrate material (402) (equate to 102) which is passed between both rollers (418 and 414).

- In general, the pressure or feed rollers (416 and 418) must have an insulating outer surface that prevents short circuits at the anode and cathode (412 and 414).

With said arrangement of the rollers (412, 414, 416 and 418), a semi-hermetic cavity (440) can be formed between the outer surfaces of the four rollers (412, 414, 416 and 418) to delimit the treatment area (124) and contain the plasma. The entire cavity (440) may comprise a first section ("right") (440a) in the space between the upper, right and lower rollers (412, 416 and 414) and a second section ("left") (440b) in the space between the upper, left and lower rollers (412, 418 and 414). The solid circle at the end of the line indicating the right section (440a) of the cavity (440) represents the gas flow in the cavity. The solid rectangle at the end of the line indicating the left section (440b) of the cavity (440) represents the laser beam (132).

The plasma generated in the cavity (440) can be a plasma at atmospheric pressure (AP). Therefore, it is not necessary to seal the cavity (440). However, stops or caps (not shown) can be placed at the ends of the rollers (412, 414, 416 and 418) to contain (semi-enclosed) and control the flow of gas into and out of the cavity (440).

FIG. 4B illustrates an embodiment (400B) in which the left and right rollers (416 and 418) are slightly separated from the other two rollers (412 and 414), so that the cavity (440) is open and allows the thicker and more rigid substrate processing. However, this requires an independent and direct actuation of each electrode (anode and cathode). The material would be conducted through the reaction zone through external feed and output rollers.

FIG. 4C illustrates an embodiment (400C) in which an inverted "U" shaped screen (420) is used, instead of the left and right rollers (416 and 418), to delimit the cavity (440), which It is divided between a right section and a left section (440a and 440b). The screen (420) is essentially arranged completely covering a roller (412) (except where the material is driven) and at least part of the other roller (414). A second screen (not shown) could be placed under the lower roller (414).

FIG. 4D illustrates an embodiment (400D) adapted to treat rigid substrates. The substrate (402) described previously was flexible, such as a textile material. Rigid substrates, such as glass for touch screens, can also be treated with hybrid plasma and precursor materials. A rigid substrate (404) with an upper face (404a) and a lower face (404b) passes through the upper roller (e1) (412) and the lower roller (e2) (414). A row of nozzles (422) (equal to 322) may be arranged to supply precursor material in liquid, solid or atomized form. A screen (not shown) similar to that indicated with reference 420 (see FIG. 4C) may also be incorporated to contain the hybrid plasma.

FIG. 4E shows a design (400E) that incorporates a row of high voltage plasma nozzles (injectors) (430) instead of the cylindrical electrodes (e1 and e2). For example, ten injectors (430) with a separation of 20 cm from each other can be arranged in the treatment area (124). The illustration shows a rigid substrate (404). A row of nozzles (422) (equate to 322) can be placed to supply the precursor material, for example, in atomized form, in the

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substrate (404) in a pretreatment area (122) before exposure to hybrid plasma. For example, ten nozzles (422) with a separation of 20 cm from each other in the pretreatment area (122) can be arranged. A screen (not shown) similar to that indicated with reference 420 (see FIG. 4C) may also be incorporated to contain the hybrid plasma.

This design allows to treat metallic substrates and other conductive substrates.

FIG. 4F illustrates an embodiment (400F) with a first roller ("upper") (412) that functions as an electrode (e1) (or anode), a second roller ("lower") (414) that functions as an electrode (e2 ) (or cathode) and two pressing rollers (436 and 438) (equate to 416 and 418).

In contrast to embodiment 400A (FIG. 4A), in this embodiment, the pressing rollers (436 and 438) are slightly separated (for example, 1 cm) from the upper and lower rollers (412 and 414). Therefore, although they will continue to contribute to the plasma, they may not be able to function as feed rollers and other feed rollers may have to be placed (not shown).

The right roller (436) (equate to 416) is shown with a coating or lining (437) on the surface. The left roller (438) (equate to 418) is shown with a coating (439) on the surface. The right and left rollers (436 and 438) of the hybrid plasma treatment area (124) can, for example, be wrapped with a metal sheet (or incorporate a metal outer layer) that can be detached during the process by the hybrid plasma with high energy content or by the laser (second source of energy), creating a column that contains reactive metal plasma and can easily be fixed to the surface radicals of the substrate to create nanometric coatings with a metal composition in the substrate material. The metallic material (sheet, layer) can be subject to plasma controlled etching or ablation and the detached metal components can react with the plasma and deposit on the substrate, for example, in nanometric scale layers.

The metallic material that covers both rollers (436 and 438) may consist, for example, of titanium, copper, aluminum, gold or silver, or a combination of these. It is possible to coat one of the rollers with one material and the other roller, with another material. It is also possible to cover different parts of the rollers (436 and 438) with different materials. In general, when ablation of these materials occurs, they form a vapor-shaped precursor material in the treatment area (124) (unlike the nozzle system 322 and 422 that supply precursor material in the pretreatment area [124 ]).

Additional characteristics

Although not expressly shown, the finishing materials dispensed in the substrate (102) after treatment by a hybrid energy (124) can be immediately exposed to secondary plasma or hybrid plasma in order to dry or seal the finished materials that have been dispensed after surface activation by means of hybrid plasma or in order to achieve a reaction in said materials.

Although not expressly shown, it should be understood that various gases, such as 02, N2, H, CO2, Ar or He, or compounds, such as silane or siloxane-based materials, can be introduced into the plasma, for example, in the area of treatment (124), to provide different characteristics and desired properties to the treated substrate.

To provide antimicrobial properties to the treated material, precursor materials, such as silanes or siloxanes without silver base and materials of the aluminum chloride family, such as dimethyloctadecyl chloride [3- (trihydroxysilyl) propyl] ammonium can be incorporated. Other groups of silanes or siloxanes can be used to affect hydrophobicity, as well as siloxones and ethoxysilanes (to increase hydrophilicity). The hexamethyldisiloxane applied in the plasma in the gas phase can smooth the surface of the textile fibers and increase the contact angle, which is indicative of the level of hydrophobicity.

It is possible to use a small negative pressure or a partial vacuum at atmospheric pressure to drag the plasma components towards the porous substrates and achieve greater penetration of said components into these substrates. FIG. 3 shows said suction system, such as a plate (base) (324) over which the substrate (102) passes in the treatment area (124) and which can have several holes and be properly connected to a suction system ( not shown) to achieve the desired effect. The plate (324) can function as one of the electrodes that generate the plasma. Alternatively, to carry out this function, a roller or similar element could be easily modified (with holes and connected to the suction system).

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It should be understood that it is a dry process with a low environmental impact, and that the leftover gases or components are inherently safe and can be evacuated from the system and recycled or disposed of as appropriate.

A method is therefore described for treating materials with at least two energy sources in which said sources consist of: 1) an AP plasma generated by the passage of several gases through a high energy electromagnetic field and 2) at least one laser that interacts with said plasma to create a "hybrid plasma". The laser can operate in the range of ultraviolet wavelengths: at 308 nm or less. The laser can be an excimer laser that operates with an output power of at least 25 W, even at more than 100 W, more than 150 W and more than 200 W. The laser can be pulsed, for example, at a frequency 25 Hz or higher, such as 350-400 Hz, including picosecond and femtosecond lasers. Although only the interaction of a laser with the plasma (and the substrate) has been described, the invention contemplates the possible use of two or more lasers.

Some examples of parameters to generate the plasma in the treatment area are: 1-2 kW for the plasma generated at high voltage and 500 mJ and 350 Hz for the ultraviolet laser at 308 nm, in a mixture of 80% argon gases and oxygen or 20% CO2.

In addition to the laser, an ultraviolet source, such as an ultraviolet lamp or an array of high power ultraviolet LEDs (light emitting diodes) arranged along the treatment area, can be used to direct the energy to the plasma AP and thus create a hybrid plasma and to interact with the material being treated (recording it or generating reactions or synthesis).

In the main description, the treatment of a face (102a) of a substrate material (102) has been illustrated and some examples of treatments have been described. The invention contemplates that the opposite lower face (102b) of the material (102) can also be treated, for example, by passing the material (102) back through the treatment area (124). To treat the second side of the material, various energy sources and different environments can be used, as well as different precursor and finishing materials. In this way, both sides of the material can be treated. It should also be understood that the treatments can exceed the surface of the material in question to modify or improve the properties of the interior (the core) of the material. In some cases, both sides of the material and its interior can be treated effectively from one side.

The system can also be used to treat materials that are not in the form of a sheet, sheet or roll fabric. For example, the system can be used to improve the optical and morphological properties of organic light emitting diodes (OLEDs) by annealing with hybrid energy. These independent items can be transported through the system in any way that is appropriate.

Other types of energy may be applied in a combined or consecutive manner to improve the processing capacity. For example, the method of treating materials can use a combination of at least two energy sources, such as microwaves and lasers, microwaves and plasma generated by electromagnetic means, plasma and microwaves or different combinations of plasma, lasers and electron cyclotron resonance (ECR , for its acronym in English) with pulsed microwaves.

The two energy sources can consist of 1) an atmospheric plasma that uses different ionized gases that cross high-energy electromagnetic fields, and 2) an ultraviolet light source that generates and directs radiation to the strongly ionized plasma and directly to the surface that It will be treated. The ultraviolet light source may consist of a matrix of high power ultraviolet LEDs arranged along the treatment area. The high power ultraviolet LEDs can interact with the plasma to increase its energy, in addition to acting directly on the substrate in order to achieve etching or a reaction on said substrate.

An automated material handling system can transport the material in a controlled manner by the energy fields created by combining the energy sources.

A series of steps can be performed in the process, such as:

Step 1 (optional): precursor application

Step 2: exposure to hybrid energy

Step 3 (optional): application of precursor or finishing material

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Step 4: exposure to hybrid energy

In this process, all steps would be performed consecutively immediately within the system.

The invention contemplates the introduction of a delivery system into the process capable of adding precursor materials in the gas or steam phase directly into the plasma reaction zone.

Some examples of treatment process parameters

Treatment 1: hydrophilicity

Precursor material

Hydroxy fraction of polydimethylsiloxane (PDMS hydroxy fraction)

Alt .: copolymer (dimethylsiloxane and / or with dimethylsilane mixture)

To be

Frequency 250 Hz Power 380 mJ Plasma

Argon carrier gas 80%

Reactive gas O2 20%

Flow rate 15 l / min Pressure slightly higher than 1 bar

Power 2 kW

Treatment 2: Precursor dyeability

Without precursor or other Laser precursor catalysts

Frequency 250 Hz

Power 380 mJ Plasma

Argon carrier gas 80%

Reactive gas O2 or N2 20%

Flow rate 15 l / min Pressure slightly higher than 1 bar

Power 2 kW

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Treatment 3: hydrophobicity

Precursor Mixture of octamethylcyclotetrasiloxane / polydimethylsilane (water soluble polymethylhydrosiloxane

mixed with polydimethylsiloxane with water-soluble polyglycol ether or a combination of the above with polydimethylsiloxane). The use of water-soluble mixtures allows the materials to be diluted with deionized water to the necessary concentrations depending on the application, the cost-effectiveness and the results obtained. Water-soluble mixtures can be made with the corresponding additives: essentially, these are methods for mixing the oil with water in order to create emulsions, which are generally defined according to the size of the emulsion dispersant, that is, as a macro or micro (macro> 100 pm, micro <30 pm).

Alt .: copolymer (dimethylsiloxane and / or with dimethylsilane mixture)

To be

Frequency at least 350 Hz

Power at least 450 mJ

Plasma

Carrier gas nitrogen, argon, helium 80%

CO2 or N2 reactive gas 2-20%

Flow rate 10-40 l / min Pressure slightly higher than 1 bar Power 0.5-1 kW

Treatment 4: Precursor flame retardant properties

Copolymers and terpolymers based on siloxane / silane and polyborosiloxane with key inorganic compounds, essentially transition oxides of titanium, silicon and zirconium, and boron. Boron is also included with siloxane copolymers and terpolymers, such as organosilicon / oxyethyl modified polyborosiloxane. Some recent phosphorus mixtures based on limited material compositions may be used, depending on the types of sutrate materials and the expected results. Mixtures of water soluble octamethylcyclotetrasiloxane / polydimethylsilane mixed with polydimethylsiloxane with water soluble polyglycol ether or a combination of the above with polydimethylsiloxane can be used with the following additives:

- Calcium metaborate additive to silane / siloxane

- Silane / Siloxane Silicon Oxide Additive

- Titanium tetraisopropanolate additive

- Titanium dioxide (rutile)

- Ammonium Phosphate

- Aluminum oxide

- Zinc Borate

- Boron phosphate with preceramic oligomers

- Aerogels and hydrogels, cross-linked polyacrylates of low or high density

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Compositions encapsulated on a nanometric / micrometric scale

Example: Dimethylsiloxane, alternatively or additionally with dimethylsilane and with polyborosiloxane, with transition oxides added in a concentration of between 5 and 10%, such as TiO2, SiO2 (in pyrogenic, gel or amorphous form), Al2O3, etc. The indicated precursor materials can improve the flame retardant properties of the materials in the system described herein using a hybrid plasma (eg, with laser). The invention contemplates the possibility that the precursor materials indicated herein improve the flame retardant properties (or other properties) of the materials in material treatment systems using a non-hybrid plasma (e.g., without laser) .

To be

Frequency at least 350 Hz

Power at least 450 mJ

Plasma

Carrier gas nitrogen, argon, helium 80%

CO2 or N2 reactive gas 2-20%

Flow rate 10-20 l / min Pressure slightly higher than 1 bar Power 0.5-1 kW

Treatment 5: Precursor antimicrobial properties

of dimethyloctadecyl [3- water mixed with

polydimethylsiloxane with water-soluble polyglycol ether or a combination of the above with polydimethylsiloxane, with the following additives:

- Dimethyloctadecyl chloride [3- (trimethoxysilyl) propyl] ammonium

- Chitosan

Mixtures of siloxane / silane according to the hydrophobicity base, with the addition of (trimethoxysilyl) propyl] ammonium chloride. Mixture of octamethylcyclotetrasiloxane / polydimethylsilane soluble in

To be

Frequency at least 350 Hz

Power at least 450 mJ

Plasma

Carrier gas nitrogen, argon, helium 80%

CO2 or N2 reactive gas 2-20%

Flow rate 10-20 l / min Pressure slightly higher than 1 bar Power 0.5-1 kW

Claims (15)

5 10 fifteen twenty 25 30 35 40 Four. Five fifty 55 60 1. A method for the treatment of a substrate (102,402,404) consisting of: A high voltage (HV) of alternating current (AC) and atmospheric pressure (AP) is created for the treatment of plasma in the area (124) comprising two electrodes separated from each other (e1 / e2; 212/214; 412 / 414) where the electrodes are provided with the first and second roller (212/214; 412/414) located in parallel with each other, with a gap between them, the gap corresponds to the thickness of the substrate, which allows the substrate to feed on the rollers , characterized in that the method consisting of: At least one laser beam (132) is directed into the area under treatment, approximately parallel between the electrodes and slightly above the top surface (102a) of the substrate, which interacts with the plasma, creating a hybrid plasma; wherein at least one laser beam is directed at an angle (a) of less than 1-10 degrees where the upper part of the substrate is being treated to be directly irradiated and coincidentally reacts with the plasma being generated by the two electrodes; and creating a hybrid plasma that interacts with the substrate in the treated area (124). 2. The method of claim 1, wherein the laser has at least one of the following characteristics: The laser contains an excimer laser; The laser operates with an ultraviolet (UV) wavelength; The laser operates with at least 25 watts of output power. 3. The method of the preceding claims consists of: A pretreatment of the substrate, dispensing (122,322,422) precursor materials (323,437) on the substrate. 4. The method of the preceding claims consists of: After treating the substrate, it dispenses (126,326,426) finished materials (327,439) onto the substrate. 5. The method of the preceding claims, wherein the substrate is a selected material consisting of a synthetic textile material, polyester, an organic material, cotton and wool. 6. The method of the preceding claims, wherein at least one laser beam has a rectangular cross-sectional shape showing a consistent power density over the total treated area. 7. The device (100,400 A, 400 B, 400 C, 400 D, 400E, 400 F) for treating materials comprises: Two electrodes separated from each other (e1 / e2; 212/214; 412/414) to generate a plasma in the region under treatment (124); where the two electrodes of the first and second rollers are placed in parallel with a gap between them, the gap corresponds to the thickness of the substrate, to allow the material to be fed between the rollers. It is characterized in that the device comprises: One or more lasers (130) correspondingly targeting one or more rays (132) within the treated area when interacting with the plasma and the material being treated; by this means at least one laser beam is directed at an angle (a) of less than 1-10 degrees where the upper part of the substrate is being treated to be directly irradiated and coincidentally reacts with the plasma being generated by the two electrodes. 8. The device of claim 7 comprises: Three or four rollers (416/418) where the first and second rollers are placed adjacently forming a tight cavity (440) between the outer surfaces of the first, second, third and fourth rollers (412,414,416,418) to define the treatment area (124) and to contain the plasma. 9. The device of claim 8, wherein: at least the third or fourth roller (436/438) comprises a metal outer layer (437/439). 10. The device of claim 7, further comprising: 10 fifteen twenty A plate (420) placed around the first and second roller (412/414) defining semi-tight cavity (440). 11. The device of claims 7 to 10, further comprising at least: One of the nozzles (322/422) for the emission of the precursor material, in liquid, solid or atomized form; and the nozzles (326) for dispensing the final material (327) into the material being treated. 12. The device of claim 7, wherein the electrodes (e1 / e2; 212/214; 412/414) are coated with ceramic. 13. The device of claims 7 to 12 wherein at least one of the laser beams has a rectangular cross-sectional shape showing a consistent power density over the total treated area. 14. The use of the device according to claims 7 to 13 is for treating the textile substrate consisting of: a synthetic textile material, polyester, an organic material, cotton or wool. 15. The textile material is obtained by the methods detailed in claim 1 to 6.