Patent Description:
Development of "smart textiles" has been an active area of interest to improve various properties such as stain resistance, waterproofing, colorfastness and other characteristics achievable through advanced treatment using plasma technologies, microwave energy sources and in some cases, chemical treatments.

Atmospheric Plasma Treatment (APT) improves fiber surface properties such as hydrophilicity without affecting the bulk properties of these fibers, and can be used by textile manufacturers and converters to improve the surface properties of natural and synthetic fibers to improve adhesion, wettability, printability, dyeability, as well as to reduce material shrinkage.

Atmospheric-pressure plasma (or AP plasma or normal pressure plasma) is the name given to the special case of a plasma in which the pressure approximately matches that of the surrounding atmosphere. AP plasmas have prominent technical significance because in contrast with low-pressure plasma or high-pressure plasma no cost-intensive reaction vessel is needed to ensure the maintenance of a pressure level differing from atmospheric pressure. Also, in many cases these AP plasmas can be easily incorporated into the production line. Various forms of plasma excitation are possible, including AC (alternating current) excitation, DC (direct current) and low-frequency excitation, excitation by means of radio waves and microwave excitation. Only AP plasmas with AC excitation, however, have attained any noteworthy industrial significance.

Generally, AP plasmas are generated by AC excitation (corona discharge) and plasma jets. In the plasma jet, a pulsed electric arc is generated by means of high-voltage discharge (<NUM>-<NUM> kV, <NUM>-<NUM>) in the plasma jet. A process gas, such as oil-free compressed air flowing past this discharge section, is excited and converted to the plasma state. This plasma then passes through a jet head to arrive on the surface of the material to be treated. The jet head is at earth potential and in this way largely holds back potential-carrying parts of the plasma stream. In addition, the jet head determines the geometry of the emergent beam. A plurality of jet heads may be used to interact with a corresponding area of a substrate being treated. For example, sheet materials having treatment widths of several meters can be treated by a row of jets.

AP and vacuum plasma methods have been utilized to clean and activate surfaces of materials in preparation for bonding, printing, painting, polymerizing or other functional or decorative coatings. AP processing may be preferred over vacuum plasma for continuous processing of material. Another surface treatment method utilizes microwave energy to polymerize precursor coatings.

<CIT>, <CIT>, <CIT> and <CIT> represent prior art documents related to the field of the treatment of substrates with hybrid plasma; the German document discloses the treatment of textiles, the international patent application and the US laid open the treatment of fibers and the Japanese document does not specify the substrate treated.

The invention is generally directed to providing improved techniques for treatment (such as surface treatment and modification) of materials, such as substrates, more particularly such as textiles (including woven or knitted textiles and non-woven fabrics), and broadly involves the combining of various additional energy sources (such as laser irradiation) with high voltage generated plasma(s) (namely atmospheric pressure (AP) plasmas) for performing the treatments, which may alter the core of the material being treated, as well as the surface, and which may use introduced gases or precursor materials in a dry environment. Combinations of various energy sources are disclosed.

An embodiment of the invention broadly comprises a method according to claim <NUM> to treat and produce technical textiles and other materials utilizing at least two combined mutually interacting energy sources such as laser and high voltage generated atmospheric (AP) plasma.

The techniques disclosed herein may readily be incorporated into a system for the automated processing of textile materials. Functionality may be achieved through non-aqueous cleaning like etching or ablating, activating by way of radical formation on the surface(s) and simultaneously and selectively increasing or decreasing desired functional properties. Properties such as hydrophobicity, hydrophilicity fire retardancy, anti-microbial properties, shrink reduction, fiber scouring, water repelling, low temperature dyeing, increased dye take up and colorfastness, may be enabled or enhanced, increased or decreased, by the process(es) which produces chemical and/or morphological changes, such as radical formation on the surface of the material. Coatings of material, such as nano-scale coatings of advanced materials composition may be applied and processed.

Combining (or hybridizing) AP plasma energy with one or more additional (or secondary) energy sources such as a laser, X-ray, electron beam, microwave or other diverse energy sources may create a more effective (and commercially viable) energy milieu for substrate treatment. The secondary energy source(s) is applied in combination (concert, simultaneously) with the AP plasma energy to achieve desired properties.

Secondary energy sources may act upon the separately generated plasma plume and produce a more effective, energetic plasma milieu, while also having the ability to act directly on the surface and in some cases, the core of the material subjected to this hybrid treatment.

According to the invention the material being treated is any of non-rolled fabrics, pieces of fabric material, loose fibers and membrane substrates, the material being treated disposed on a carrier membrane. The techniques disclosed herein may be applicable to the treatment of textiles (both organic and inorganic), paper, synthetic paper, plastic and other similar materials which are typically in flat sheet form ("yard goods"). The techniques disclosed herein may also be applied to the processing of plastic or metal extrusion, rolling mills, injection molding, spinning, carding, weaving, glass making, substrate etching and cleaning and coating of any material as well as applicability to practically any material processing technique. Rigid materials such as flat sheets of glass (such as for touch screens) may be treated by the techniques disclosed herein.

According to one aspect of the present invention, there is provided a method according to claim <NUM>, for treating a material comprising:.

Some advantages of the present invention may include, without limitation, a method of creating a more energetic and effective plasma to clean and activate surfaces for subsequent processing or finishing. For example, ultra-violet (UV) laser radiation, either continuous wave (CW) or pulsed, may be combined with electromagnetically generated AP plasma to create a more highly ionized and energetic reaction milieu for treating surfaces. The resulting hybridized energy may have effects that are greater than the sum of its individual parts. Pulsed laser energy may be used to drive the plasma, creating waves, and the laser energy accelerates the resultant plasma waves which act upon the substrate like waves crashing on the beach.

The accelerated and more energetic plasma may initiate radicals in the fiber or surface of the treated substrate and attach ionized groups to the initiated radicals. Attachment of such functional groups as carboxyl, hydroxyl or others to the surface increasing polar characteristics may result in greater hydrophilicity and other desirable functional properties.

The invention advantageously combines energy sources in a controlled atmospheric environment in the presence of a material substrate. The net result may be conversion and material synthesis in the surface of the substrate - the substrate may be physically changed, in contrast with simply being coated.

In an exemplary embodiment, a high frequency RF plasma is created in an envelope (or cavity, or chamber) formed between rotating and driven rollers which extend across the width of the processing window. The plasma field generated is consistent across the width of a treatment area, and operates at atmospheric pressure. A high power Ultra Violet (UV) laser is provided for interacting with the plasma and may be with the material being treated. The beam from the laser may be shaped to have a rectangular cross-section exhibiting a consistent power density over the entire treatment area. A gas delivery system may be used to combine any combination of a plurality (such as <NUM>) of environmental gases and precursors into a single feed which populates the hybrid plasma chamber. Additionally, a spray or misting delivery system may be provided, capable of applying a thin, consistent layer of sol-gel or process accelerants to the material being treated, either pre- or post-processing.

The process of combining plasma and photonics (such as UV laser) is dry, is carried out at atmospheric pressures and uses safe and inert gases (such as Nitrogen, Oxygen, Argon & Carbon Dioxide). Changing the power intensity of the laser and the plasma, and then varying the environmental gases or the addition of sol-gels and/or other organic or inorganic precursors - i.e., changing the "recipe" - allows the system to generate a wide variety of process applications.

There are several applications for the process, including: cleaning, preparation and performance enhancement of materials.

In some exemplary embodiments, a method for treating a material comprises: creating a plasma using a first energy source in a process chamber having a treatment region; and feeding the material through the treatment region; and further comprises: directing at least one second energy source which is different than the first energy source into the plasma to interact with the plasma, resulting in a hybrid plasma; it is characterized by causing the hybrid plasma to interact with the material being treated in the treatment region. The method may further comprise feeding the material being treated to the process chamber through a twitcher system. The material being treated is any of non-rolled fabrics, pieces of fabric material (<NUM>), loose fibers (<NUM>) and membrane substrates, disposed on a carrier membrane. Prior to feeding the material (<NUM>, <NUM>, <NUM>) through the process chamber, precursors or accelerants may be applied to the carrier membrane as either (i) a spray, (ii) through roller deposition, (iii) through electrostatic discharge or (iv) a bath through which the substrate is passed. Treatment may comprise one or more of (i) reacting the precursors or accelerants in the treatment region to become incorporated with (into or onto) the substrate; (ii) reacting the precursors or accelerants directly with the substrate; and (iii) reacting gases and chemistry in the plasma with the substrate. For each of the treatments, different process parameters may be employed to selectively achieve desired results. Different sequences and combinations of the process parameters may be employed on a given material being treated. Electrostatic deposition may be used to dope fabrics or yard goods materials with dopants before they enter the process chamber. Dopants may comprise oxide powders or natural or synthetic fibers applied to the surface of the substrate material. Oriented fibers or pre-doped fibers may be applied to the substrate surface (material being treated). The treatment may alter the topographical structure of materials which comprise individual fibers or fibers or yarns within a woven or knitted fabric. Different treatments may be performed on each side of a material being treated. A material being treated may be passed several times through the treatment region, using the same or different precursors or different process parameters. Multiple energy sources may be used simultaneously to react with different elements within the substrate material. A bank of laser beams may impinge on the plasma and/or material being treated.

Reference may be made in detail to embodiments of the disclosure, some non-limiting examples of which may be illustrated in the accompanying drawing figures (FIGs). The figures are generally diagrams. Some elements in the figures may be exaggerated (not to scale with respect to other elements), others may be omitted, for illustrative clarity. The relationship(s) between different elements in the figures may be referred to by how they appear and are placed in the drawings, such as "top", "bottom", "left", "right", "above", "below", and the like. It should be understood that the phraseology and terminology employed herein is not to be construed as limiting, and is for descriptive purposes only.

The invention relates generally to treatment (such as surface treatment) of materials (such as textiles) to modify their properties.

Various embodiments will be described to illustrate teachings of the invention(s), and should be construed as illustrative rather than limiting. Although the invention is generally described in the context of various exemplary embodiments, it should be understood that it is not intended to limit the invention to these particular embodiments. An embodiment may be an example or implementation of one or more aspects of the invention(s). Although various features of the invention(s) may be described in the context of a single embodiment, the features may also be provided separately or in any suitable combination with one another. Conversely, although the invention(s) may be described in the context of separate embodiments, the invention(s) may also be implemented in a single embodiment.

According to the invention, surface treatment any of non-rolled fabrics, pieces of fabric material (<NUM>), loose fibers (<NUM>) and membrane substrates will be discussed. One or more treatments, including but not limited to material synthesis, may be applied to one or both surfaces of the textile substrate, and additional materials may be introduced. As used herein, a "substrate" may be a thin "sheet" of material having two surfaces, which may be termed "front" and "back" surfaces, or "top" and "bottom" surfaces.

The following embodiments and aspects thereof may be described and illustrated in conjunction with systems, tools and methods which are meant to be exemplary and illustrative, not limiting in scope. Specific configurations and details may be set forth in order to provide an understanding of the invention(s). However, it should be apparent to one skilled in the art that the invention(s) may be practiced without some of the specific details being presented herein. Furthermore, well-known features may be omitted or simplified in order not to obscure the descriptions of the invention(s).

<FIG> is not part of the invention but included for illustrative purposes. It shows an overall surface treatment system <NUM> and method of performing treatment, such as a surface treatment of a substrate <NUM>. In the figures presented herein, the substrate <NUM> will be shown advancing from right-to-left through the system <NUM>.

The substrate <NUM> may for example be a textile material and may be supplied as "yard goods" as a long sheet on a roll. For example, the substrate to be treated may be fibrous textile material such as cotton/polyester, approximately <NUM> meter wide, approximately <NUM> thick, and approximately <NUM> meters long.

A section 102A, such as a <NUM> x <NUM> section of the substrate <NUM> which is not yet treated is illustrated paying out from a supply reel R1 at an input section 100A of the system <NUM>. From the input section 100A, the substrate <NUM> passes through a treatment section <NUM> of the apparatus <NUM>. After being treated, the substrate <NUM> exits the treatment apparatus <NUM>, and may be collected in any suitable manner, such as wound up on a take-up reel R2. A section 102B, such as a <NUM> x <NUM> section of the substrate <NUM> which has been treated is illustrated being wound onto an take-up reel R1 at an output section 100A of the system <NUM>. Various rollers "R" may be provided between (as shown) and within (not shown) the various sections of the system <NUM> to guide the material through the system.

The treatment section (or process chamber) <NUM> may generally comprise three regions (or areas, or zones):.

The treatment region <NUM> may comprise components for generating a high voltage (HV) alternating current (AC) atmospheric plasma (AP), the elements of which are generally well known, some of which will be described in some detail hereinbelow.

A laser <NUM> may be provided, as the secondary energy source, for providing a beam <NUM> which interacts with the AP in the main treatment region <NUM>, and which may also impinge on a surface of the substrate <NUM>.

A controller <NUM> may be provided for controlling the operation of the various components and elements described hereinabove, and may be provided with the usual human interfaces (input, display, etc.).

<FIG> shows a portion of and some operative elements within the main treatment region <NUM>. Three orthogonal axes x, y and z are illustrated. (In <FIG>, the corresponding x and y axes are illustrated.

Two elongate electrodes <NUM> (e1) and <NUM> (e2) are shown, one of which may be considered to be a cathode, the other of which may be considered to be an anode. These two electrodes e1 and e2 are disposed generally parallel with one another, extending parallel to the y axis, and spaced apart from one another in the x direction. For example, the electrodes e1 and e2 are formed in the form of a rod, or a tube or other rotatable cylindrical electrode material, and are spaced apart from one another nominally, a distance sufficient to allow for clearance of the thickness of the material processed. The electrodes e1 and e2 may be disposed approximately <NUM> above the top surface 102a of the substrate <NUM> being treated.

The electrodes e1 and e2 may be energized in any suitable manner to create an atmospheric plasma (AP) along the length of the resulting cathode/anode pair in a space between and immediately surrounding the electrodes e1 and e2, which may be referred to as a "plasma reaction zone".

As mentioned above, a laser beam <NUM> may be directed into the main treatment region <NUM>, and may also impinge on a surface of the substrate <NUM>. Here, the laser beam <NUM> is shown being directed approximately along the y axis, approximately parallel to and between the electrodes e1 and e2, and slightly above the top surface 102a of the substrate <NUM>, so as to interact with the plasma (plume) generated by the two electrodes e1 and e2. In an exemplary application, the beam footprint may be a rectangle approximately <NUM> x <NUM>. The beam may be oriented vertically or horizontally to best achieve the desired interaction of plasma and/or direct substrate irradiation
The laser beam <NUM> may be directed minutely but sufficiently "off angle" to directly irradiate the substrate <NUM> to be treated as it coincidently reacts with the plasma being generated by the two electrodes e1 and e2. More particularly, the laser beam <NUM> may make an angle of "a" which is approximately <NUM> degrees with the top surface 102a of the substrate <NUM> so as not to impinge on its surface 102a. Alternatively, the laser beam <NUM> may make an angle of "a" which is approximately less than <NUM> - <NUM> degrees with the top surface 102a of the substrate <NUM> so as to impinge on its surface 102a. Other orientations of the beam <NUM> are possible, such as perpendicular ("a" = <NUM> degrees) with the surface 102a of the substrate <NUM>. The laser beam <NUM> may be scanned, using conventional galvanometers and the like, to interact with any selected portion of the plasma generated by the two electrodes e1 and e2 or the substrate <NUM>, or both.

The plasma is created using as a first energy source a high voltage (HV) alternating current (AC). A second, different energy source (such as laser) is caused to interact with the plasma, resulting in a "hybrid plasma", and the hybrid plasma is caused to interact (in a treatment region) with the substrate (material) being treated. In addition to interacting with the first energy source, the second energy source can be caused to also interact directly with the material being treated. The direct interaction with the substrate or other gas (secondary or precursor) may produce its own laser sustained plasma which in turn may further interact with the high voltage generated plasma to more highly energize the reaction milieu.

The substrate <NUM> (material being treated) may be guided by rollers as it passes through the main treatment region (area) <NUM>. <FIG> illustrates that one of these rollers <NUM> may serve as the anode, and the other roller <NUM> may serve as the cathode (or vice-versa) of a cathode/anode pair for generating the plasma. It may be noted that in <FIG>, the substrate <NUM> is disposed to one side of (below, as viewed) both of the two electrodes e1 and e2, and in <FIG> the substrate <NUM> is disposed between the two electrodes e1 and e2. In both cases, the plasma created by the electrodes e1 and e2 acts on at least one surface of the substrate <NUM>. The anodes and cathodes may be coated with an insulating material, such as ceramic.

It should be understood that the invention is limited to the electrodes e1 and e2 being first and second rollers disposed parallel to each other with a gap therebetween, to allow the material being treated to be fed between the rollers. Furthermore, for example, as a non-claimed alternative to using two electrodes e1 and e2, a row of plasma jets (not shown) delivering a plasma may be provided to create the desired plasma above the surface 102a of the substrate <NUM>.

<FIG> shows that in the pre-treatment region (area) <NUM>, a row of spray heads (nozzles) <NUM> covering the full width of the material to be treated, or other suitable means, may be used to dispense precursor materials <NUM> in solid, liquid or gaseous phase onto the substrate <NUM> to enable the processing of/for specific properties such as antimicrobial, fire retardant or super-hydrophobic/hydrophilic characteristics.

There may be an intermediate "buffer" zone between the pre-treatment region (area) <NUM> and the main treatment region (area) <NUM>, to allow time for the materials applied in pre-treatment to soak into (be absorbed by) the substrate. The process still runs a single length of material, but the buffer may hold, for example, up to <NUM> of fabric. For example, when material being treated (such as yard goods) is feeding through the system at <NUM> meters/min, this would allow for several minutes "drying time" between pre-treatment (<NUM>) and hybrid plasma treatment (<NUM>), without stopping the flow of material through the system.

Similarly, in the post-treatment region (area) <NUM>, a row of spray heads (nozzles) <NUM> covering the full width of the material which was treated (<NUM>), or other suitable means, may be used to dispense finishing materials <NUM> in solid, liquid or gaseous phase onto the substrate <NUM> to imbue it with desired characteristics.

<FIG> and <FIG> illustrate various embodiments of elements in the treatment region <NUM>.

<FIG> illustrates an embodiment 400A wherein:.

With such an arrangement of rollers <NUM>, <NUM>, <NUM>, <NUM>, a semi-airtight cavity ("<NUM>") may be formed between the outer surfaces of the four rollers <NUM>, <NUM>, <NUM>, <NUM> for defining the treatment region <NUM> and containing the plasma. The overall cavity <NUM> may comprise a first ("right") portion 440a in the space between the top, right and bottom rollers <NUM>, <NUM>, <NUM> and a second ("left") portion 440b in the space between the top, left and bottom rollers <NUM>, <NUM>, <NUM>. The filled circle at the end of the lead line for the right portion 440a of the cavity <NUM> represents gas flow into the cavity. The filled rectangle at the end of the lead line for the left portion 440b of the cavity <NUM> represents the laser beam (<NUM>).

The plasma generated in the cavity <NUM> is an atmospheric pressure (AP) plasma. Therefore, sealing of the cavity <NUM> is not necessary. However, end caps or plates (not shown) may be disposed at the ends of the rollers <NUM>, <NUM>, <NUM>, <NUM> to contain (semi-enclose) and control the gas flow in and out of the cavity <NUM>.

<FIG> illustrates an embodiment 400B wherein the left and right rollers <NUM> and <NUM> are moved slightly outward from the rollers <NUM> and <NUM>, thereby opening up the cavity <NUM> to allow for thicker and/or stiffer substrates to be processed. This would however require independent or direct drive of each electrode, anode and cathode. The material would be driven through the reaction zone by outside feeding and take up rollers.

<FIG> illustrates an embodiment 400C wherein a generally inverted U-shaped shield <NUM> is used instead of the left and right rollers (<NUM> and <NUM>) to define the cavity <NUM> having right and left portions 440a and 440b. The shield <NUM> is disposed substantially completely around one roller <NUM> (except for where the material feeds through), and at least partially around the other roller <NUM>. An additional shield (not shown) could be disposed under the bottom roller <NUM>.

<FIG> illustrates an embodiment 400F a first ("top") roller <NUM> operative to function as an electrode e1 (or anode), a second ("bottom") roller <NUM> operative to function as an electrode e2 (or cathode), and two nip rollers <NUM> and <NUM> (compare <NUM> and <NUM>).

In contrast with the embodiment 400A (<FIG>), in this embodiment the rollers <NUM> and <NUM> are spaced outward slightly (such as <NUM>) from the top and bottom rollers <NUM> and <NUM>. Therefore, although they will still help contain the plasma, they may not function as feed rollers, and separate feed rollers (not shown) may need to be provided.

The right roller <NUM> (compare <NUM>) is shown having a layer or coating <NUM> on its surface. The left roller <NUM> (compare <NUM>) is shown having a layer or coating <NUM> on its surface. For example, the rollers <NUM> and <NUM> in the hybrid plasma treatment region <NUM> may be wrapped with metallic foil (or otherwise have a metallic outer layer) which may be etched away, in process, by the highly energetic hybrid plasma and/or by the laser (second energy source) creating a plume containing reactive metallic plasma which may readily couple with the substrate surface radicals to create nano-layer coatings with metallic composition on the substrate material. The metallic material (foil, layer) may be controllably etched or ablated by the plasma, and the effluent metallic constituents may react with the plasma and be deposited on the substrate, such as in nano-scale layers.

The metallic material coating the rollers <NUM> and <NUM> may comprise any one or a combination of titanium, copper, aluminum, gold or silver, for example. One of the rollers may be coated with one material, the other of the rollers may be coated with another material. Different portions of the rollers <NUM> and <NUM> may be coated with different materials. Generally, when these materials are ablated, they form vapor precursor material, in the treatment region <NUM> (and may therefore be contrasted with the nozzles <NUM> and <NUM> providing precursor material in the pre-treatment region <NUM>.

Although not specifically shown, finishing materials dispensed onto the substrate <NUM> after hybrid energy treatment (<NUM>) may be subjected to an immediate secondary plasma or hybrid plasma exposure to dry, seal or react finishing materials which have been dispensed following activation of the surface by the hybrid plasma.

Although not specifically shown, it should be understood that various gases, such as O<NUM>, N<NUM>, H, CO<NUM>, Argon, He, or compounds such as silane or siloxane based materials may be introduced into the plasma, such as in the treatment region <NUM>, to impart various desired characteristics and properties to the treated substrate.

To impart anti-microbial properties to the material being treated, precursor materials may be introduced such as non-silver based silanes/siloxanes and the aluminum chloride family such as <NUM> (trihydroxylsilyl) propyldimethyl octadecyl, ammonium chloride. Other Silane/Siloxane groups may be used to affect hydrophobicity as well as siloxones and ethoxy silanes (to increase hydrophilicity). Hexamethylidisiloxane applied in the gaseous phase in the plasma may smooth the surface of textile fibers and increase the contact angle which is an indication of the level of hydrophobicity.

Negative draft or atmospheric partial vacuum may be employed to draw plasma constituents into and further penetrate the thickness of porous substrates. <FIG> shows that suction means, such as platen (bed) <NUM> over which the substrate <NUM> passes, in the treatment area <NUM>, may be provided with a plurality of holes and connected in a suitable manner to suction means (not shown) to create the desired effect. The platen <NUM> may function as one of the electrodes for generating the plasma. Alternatively, a roller or the like could readily be modified (with holes and connected with suction means) to perform this function.

It should be understood that the process is dry and has a low environmental impact, and that leftover or byproduct gases or constituents are inherently safe and may be exhausted from the system and recycled or disposed of in an appropriate manner.

There is thus provided a method of treating materials with at least two energy sources, wherein the two energy sources comprise (i) an AP plasma produced by various gases passing through a high energy electromagnetic field and (ii) at least one laser interacting with said plasma to create a "hybrid plasma". The laser may operate in the ultra-violet wave length range, at <NUM> or less. The laser may comprise an excimer laser operating with at least <NUM> watts of output power, including more than <NUM> watts, more than <NUM> watts, more than <NUM> watts. The laser may be pulsed, such as at a frequency of <NUM> or higher, such as <NUM>-<NUM>, including picosecond and femtosecond lasers. Although only one laser has been described interacting with the plasma (and the substrate), it is within the scope of the invention that two or more lasers may be used.

Some exemplary parameters for generating the plasma in the treatment region are <NUM> - <NUM> Kw (kilowatts) for the HV generated plasma and 500mjoules, <NUM> for the <NUM> UV laser, in an <NUM>% argon, <NUM>% Oxygen or CO<NUM> gas mix.

As an alternative to or in addition to using a laser, an ultraviolet (UV) source such as a UV lamp or an array of high powered UV LEDs (light-emitting diodes) disposed along the length of the treatment area may be used to direct energy into the AP plasma to create the hybrid plasma, as well as to interact with (such as to etch, react and synthesize upon) the material being treated.

In the main, hereinabove, treating one surface 102a of a substrate material <NUM> was illustrated, and some exemplary treatments were described. It is within the scope of the invention that the opposite bottom surface 102b of the material <NUM> may also be treated, such as by looping the material <NUM> back through the treatment region <NUM>. Different energy sources and milieus, precursor and finishing materials may be used to treat the second surface of the material. In this manner, both surfaces of the material may be treated. It should also be understood that the treatments may extend to within the surface of the material being treated to alter or enhance properties of the inner (core) material. In some cases, both top and bottom surfaces as well as the core of the material may be effectively treated from one side.

The two energy sources comprise (i) an atmospheric plasma, utilizing various ionized gases passed through high energy electromagnetic fields, and may comprise (ii) an ultra violet (UV) source generating and directing radiation into the highly ionized plasma and directly at the surface to be treated. The UV source may comprise an array of high powered UV LEDs (light-emitting diodes) disposed along the extent of the treatment area. The high powered ultra-violet LEDs may interact with the plasma to more highly energize the plasma, as well as acting directly on the substrate to etch or react said substrate.

An automated material handling system may controllably feed material through the energy fields produced by a combination of energy sources.

A series of process steps may be performed, such as:.

in which all steps are accomplished in serial fashion immediately within the system.

It is within the scope of the invention to introduce into the process a delivery system capable of adding gas/vapor phase precursor materials directly in to the plasma reaction zone.

Precursor
Either no precursor or other precursor catalysts
Laser.

Precursor octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluble, hydrogen methyl polysiloxane mixed with polydimethylsiloxane with polyglycolether (water soluble) or combination of the above with polydimethylsiloxane). Using water soluble blends allows for diluting the materials with de-ionised water to the required concentrations based on the application, cost effectiveness and output performance results. Water soluble blends may be produced with relevant additives - these are essentially methods for mixing oil with water to produce emulsions, generally described by the size of the emulsion dispersant, i.e. macro or micro (macro is ><NUM> microns, micro<<NUM> microns). alt: copolymer (Dimethylesiloxane and/or with blend of dimethylesilane).

Copolymers and Terpolymers based on siloxane/silane and polyborosiloxane with key inorganic compounds, essentially transition oxides of titanium, silicon and zirconium and boron. Also included, Boron containing siloxane Copolymers and Terpolymers, such as organosilicon/oxyethyl modified polyborosiloxane. Some limited material composition based recent new phosphorous blends may be used, based on the substrate material types and output requirements. Octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluble) mixed with polydimethylsiloxane with polyglycolether (water soluble) or combination of the above with polydimethylsiloxane with additives of:.

Example: dimethylsiloxane and/or with dimethylsilane with polyborosiloxane, with added transition oxides, range <NUM> to <NUM>% volume of oxides such as TiO<NUM>, SiO<NUM> (fumed, gel or amorphous), Al<NUM>O<NUM>, etc. The precursor materials set forth herein may enhance fire retardancy of materials in the system described herein utilizing a hybrid plasma (e.g., with laser).

siloxane/silane blends as per hydrophobicity platform, with the addition of octadecyldimethyl (3triethoxysilpropyl) ammonium chloride. octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluble) mixed with polydimethylsiloxane with polyglycolether (water soluble) or combination of above with polydimethylsiloxane with additives of:.

Some additional embodiments, variations of the techniques and applications for the "MLSE" (Multiplexed Laser Surface Enhancement) system described hereinabove will now be described, some of which have may have been discussed only briefly.

The system described above for illustrative purposes shows treating fabrics running roll-to-roll. The techniques disclosed herein may also be used for "yard goods", including polymeric and composite films. Also, rigid materials such as flat sheets of glass (such as for touch screens) may be treated by the techniques disclosed herein. Three-dimensional (3D) components may also be treated with the system.

According to the invention the system is modified to run non-rolled fabrics, such as pieces of fabric that are not rolled, but supplied loose, allowing "short run" fabrics such as expensive or high performance materials (including materials inherently not well-suited to roll format). As described in greater detail hereinbelow, these pieces of fabric (substrates being treated) are disposed on a carrier membrane, as described below.

<FIG> illustrates a MLSE system <NUM> using (by way of example) a configuration such as in <FIG> where the left and right rollers <NUM> and <NUM> are moved slightly outward from the (nip) rollers <NUM> and <NUM>, thereby opening up the cavity <NUM> to allow for thicker and/or stiffer substrates to be processed through the system. The material being treated, in this case a plurality of exemplary fabric substrate pieces <NUM> on a continuous carrier membrane <NUM>, may be driven through the reaction zone (energy milieu) of the system by the outside feeding and take up rollers <NUM> and <NUM> ("n1" and "n2"). The fabric pieces <NUM> on the carrier membrane <NUM> may be stretched and tensioned prior to passing through the MLSE process such as by first feeding the carrier/substrates through a traditional "twitcher" system <NUM>.

<FIG> shows that substrates <NUM> comprising fragile and loose structures and membrane substrates (such as carded wool) <NUM> can be processed (transported for treatment) through the MLSE system using a backing membrane (carrier) <NUM> of natural or manmade fabrics to support the loose structure(s) <NUM> which may be held in place on the backing membrane <NUM> by (i) the natural affinity of two materials (<NUM>, <NUM>), or (ii) electrical discharge fixing or (iii) suitable bonding media (tacky or temporary adhesive).

<FIG> shows that loose fibers <NUM>, such as individual fibers or clumps of individual fibers (e.g. raw wool), can be processed through the MLSE system using a backing membrane (carrier) <NUM> of natural or manmade fabrics to support the loose structure(s) <NUM> which may be held in place on the backing membrane <NUM> by (i) the natural affinity of two materials (<NUM>, <NUM>), or (ii) electrical discharge fixing or (iii) suitable bonding media (tacky or temporary adhesive).

Precursors or accelerants converted during the MLSE process can be pre-applied to the carrier or fabric material, and presented to the MLSE system either wet or dry. This process may be referred to as "doping". These precursors or accelerants may be applied to the carrier or fabric material as either (i) a spray, (ii) through roller deposition, (iii) through electrostatic discharge or (iv) a bath through which the carrier or fabric material is passed. Carrier or fabric material being treated can be soaked, then allowed to dry (partially or completely), then passed through the MLSE system. This may be applicable to loose fibers, fragile membranes, individual fibers.

The precursor or accelerants ("dopants") may be in the form of suspensions or solutions (for example sol-gel materials). For example octamethylcyclotetrasiloxane/polydimethylsilane blend (water soluble) and/or other silane or siloxane family of materials with additives of calcium metaborate and/or boron solutions, silicon oxide and titanium isopropoxide applied to fabrics and dried prior to MLSE treatment to effect fire retardancy. Other suitable precursors may be used to provide functionalities such as hydrophilicity, hydrophobicity or antimicrobial protection.

Where loose fibers or fragile substrates are being processed, the carrier membrane may be doped with a precursor or accelerant. During the treatment process, the carrier may lose only a portion (such as <NUM>%) of its doping, and can thus be reused a number of times before re-doping the carrier. Carriers with different dopants can be prepared in advance (and "off line"), and brought into service on an as-needed basis.

The elements within the precursor may react directly with the treated substrate or may react in the process chamber with the other environmental elements to effect the chemical and material synthesis at the surface of the substrate material.

Three treatment examples are now discussed, with respect to <FIG>, B, C. In each example, precursor material ("dopant") <NUM> is resident on (has previously been applied to) the carrier membrane <NUM> (compare <NUM>) which is supporting pieces of fabric substrate <NUM> (such as fabric material <NUM>, <NUM>) as they are transported through the process milieu, such as an atmospheric plasma <NUM> created in a treatment region (process chamber, reaction chamber, compare <NUM>). The substrate pieces <NUM> on the doped carrier <NUM> may together be considered to be an overall substrate <NUM> that may be fed through the treatment region (<NUM>).

In <FIG>, the line <NUM> indicates that precursor (or accelerant) elements <NUM> may react in the process chamber (treatment region) <NUM> to become incorporated with (into or onto) the substrate <NUM>. In <FIG>, the line <NUM> indicates that precursor elements <NUM> may react directly with the substrate <NUM>. In <FIG>, the line <NUM> indicates that process chamber elements (gases, chemistry in the plasma, as discussed above) may react directly with the substrate <NUM>. In each example, different process parameters may be employed to selectively achieve the desired results, and different sequences and combinations of the results may also readily be obtained (different sequences and combinations of the process parameters may be employed on a given substrate being treated).

Electrostatic deposition may be used to dope fabrics or yard goods materials before they enter the MLSE process chamber. For example oxide powders, natural or synthetic fibers may be applied to the surface of the substrate material. For example, oriented fibers or pre-doped fibers may be applied to the substrate surface. This process (not shown) may proceed in a manner similar to conventional "flocking" (the process of depositing many small fiber particles, called "flock", onto a surface) wherein the "flock" is given a negative charge whilst the substrate is earthed (grounded).

The MLSE process can be used to change the topographical structure of individual fibers or fibers or yarns within a woven or knitted fabric. These changes may affect/modify the physical properties of the fibers, including but not limited to strength, wear resistance, surface area etc. Generally, these topographical changes may be done independently of the aforementioned chemical changes (such as with precursor material), but can certainly be done in conjunction with those other surface treatment regimes.

The "topographical" changes to the substrate, which may also be considered to be "surface treatments", may include, but are not limited to:.

Unique structures, topography or texture can be created on the surface of the fiber, reconfiguring the substrate to produce such structures as nano brushes created on the surface of a polypropylene fiber. The topographically modified structures and fibers may be less smooth, may exhibit linear structures, and may have increased surface area which may be useful (for example) in filters such as for trapping microbes. A variety of applications for topographically modified fabrics, treated by the techniques disclosed herein, are possible.

Using solgel materials in a range of formats, treatments with a range of compositions such as metal or ceramic oxides are produced on or in the surface of the fiber substrate, either in individual fibers or fibers in a woven or knitted fabric. This also includes the use of rare earths to create "smart" functionality such as supermagnetism, electrical conductivity, sensing capabilities, etc. For example, titanium oxide may be created in the surface of polyethylene fibers using the MLSE system for self cleaning and antibacterial and durability properties.

The MLSE System can be used to create multifunctionality within a monolithic fiber, yarn, knitted fabric, woven fabric, non-woven materials or yard material. Some examples are:.

As discussed above, the laser beam may be shaped to provide a rectangular beam of consistent power density across the entire treatment area. Some further variations and enhancements are now discussed.

<FIG> show a system <NUM> comprising a block plasma generator <NUM>, a bank (such as a plurality of laser beams <NUM> beams impinging on the plasma and the material (substrate) <NUM> being treated. Multiple lasers may be used to generate the multiple beams, some individual lasers may be used to generate several of the beams.

<FIG> (compare <FIG>) shows a material substrate passing through roller electrodes e1, e2, with a bank of lasers generating beams impinging on the plasma and the material (substrate) being treated. These techniques are suitable for simple material substrates, or pieces of fabric substrate on carrier membranes, as discussed above (<FIG>).

Microencapsulation is the technology whereby chemical compounds are locked into microcapsules, whereby the capsule structure is designed to degrade under certain environmental conditions to release the stored chemical compounds. The chemical compounds can be such things as drugs and medications or dye colorants. The method of degradation may be time, heat, reaction with certain chemistries or electrical discharge. The microcapsules may be bonded to a fabric structure. The current technology uses a heat setting process in water over extended times to affix the microcapsules to the fabric weave. Thus, the capsule structure needs to be resilient enough to withstand the affixing method.

The MLSE system disclosed herein can be used to create covalent bonding of microcapsules to a substrate surface dry, either using the environmental gases or other suitable precursors, substantially instantaneously, with minimal heat dispersed into the capsule structures. This may allow for a new generation of super-sensitive microencapsulation technologies.

The process parameters of the MLSE system can be modified to produce a membrane structure over the substrate which is an atomic layer deposition. For example carbon or silicon based structures.

Claim 1:
A method for treating a material comprising:
creating a high voltage (HV) alternating current (AC) atmospheric pressure (AP) plasma (<NUM>) in a process chamber having a treatment region (<NUM>) between two spaced-apart electrodes (e1/e2; <NUM>/<NUM>; <NUM>/<NUM>),
directing at least one second energy source (<NUM>, <NUM>) which is different than the first energy source into the plasma to interact with the plasma, resulting in a hybrid plasma;
characterized by:
the electrodes being provided as first and second rollers (<NUM>/<NUM>; <NUM>/<NUM>) disposed parallel to each other with a gap therebetween, to allow the material being treated (<NUM>, <NUM>, <NUM>, <NUM>) to be fed between the rollers;
disposing the material being treated on a carrier membrane (<NUM>, <NUM>) which is driven through the treatment region and wherein the material being treated is any of non-rolled fabrics, pieces of fabric material (<NUM>), loose fibers (<NUM>) and membrane substrates;
and causing the hybrid plasma to interact with the material being treated in the treatment region.