WO2009095545A1 - Roll-to-roll method and apparatus for coating a surface - Google Patents

Roll-to-roll method and apparatus for coating a surface Download PDF

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Publication number
WO2009095545A1
WO2009095545A1 PCT/FI2009/050084 FI2009050084W WO2009095545A1 WO 2009095545 A1 WO2009095545 A1 WO 2009095545A1 FI 2009050084 W FI2009050084 W FI 2009050084W WO 2009095545 A1 WO2009095545 A1 WO 2009095545A1
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WO
WIPO (PCT)
Prior art keywords
line
nanoparticles
flexible material
treating
characteri zed
Prior art date
Application number
PCT/FI2009/050084
Other languages
French (fr)
Inventor
Jyrki MÄKELÄ
Jurkka Kuusipalo
Helmi Keskinen
Mikko Tuominen
Mikko Aromaa
Original Assignee
Maekelae Jyrki
Jurkka Kuusipalo
Helmi Keskinen
Mikko Tuominen
Mikko Aromaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Maekelae Jyrki, Jurkka Kuusipalo, Helmi Keskinen, Mikko Tuominen, Mikko Aromaa filed Critical Maekelae Jyrki
Publication of WO2009095545A1 publication Critical patent/WO2009095545A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/08—Flame spraying
    • B05D1/10—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/18—Fabrics, textiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/12—Paper, e.g. cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203—One or more of the layers being plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation

Definitions

  • the present invention relates to coating technology. Especially the present invention relates to a roll-to-roll method and apparatus for coating a flexible surface by nanoparticles .
  • Nanosized particles i.e. nanoparticles may be generated using various different methods exploiting chemical compounds as precursors. These methods include sol-gel and electrochemical methods, which can be classified as liquid phase methods. Gas phase methods include e.g. plasma spray and flame spray pyroly- sis. Aerosol-based methods such as the liquid flame spray (LFS) method may be used to generate nanoparticles from liquid precursors which are injected as small droplets through a spray head into a flame generated by a highly exothermic combustion reaction utilizing combustion gases. Combustion gases in the LFS method may be e.g. hydrogen and oxygen. Also hydrocarbons may be used to produce a flame in which case the oxygen required for the combustion reaction to take place may be obtained from air. The small precursor droplets rapidly evaporate as they come into contact with the high temperature in the flame and react with possibly other evaporated precursors to pro- cute nanoparticles.
  • LFS liquid flame spray
  • hydrocarbons may be used to produce a flame in which case the oxygen required for the combustion reaction to take place may be obtained
  • LFS the chemical reactions occurring in the flame are rapid as the combustion reaction may increase the temperature inside the flame to up to about 2500 °C .
  • the gas flow in the flame is commonly turbu- lent, which distributes the nanoparticles generated in the flame randomly in the gas flow.
  • a coating made of nanoparticles on a surface may be formed by directing the gas flow and the nanoparticle stream onto the surface.
  • LFS and other aerosol-based nanoparticle coating methods may be utilized on many different substrate materials to provide functionality on their surfaces or to otherwise modify the surface properties such as electrical conductivity or barrier properties against e.g. moisture.
  • Flame treatment is a known and widely used method for e.g. improving adhesion of plastic coating onto cardboard or paper in an extrusion coating process.
  • the method can also be used e.g. to improve printability between plastic and ink or toner.
  • methane or propane reacts with air and the flame generated by the combustion reaction oxidizes, dries and removes non-uniformities from the surface, which improves the adhesion properties of the surface.
  • methane or propane reacts with air and the flame generated by the combustion reaction oxidizes, dries and removes non-uniformities from the surface, which improves the adhesion properties of the surface.
  • By treating a plastic surface with a high temperature flame the surface is oxidized and the en- ergy of the plastic surface may be increased, which improves the printability and the coatability of the surface .
  • the purpose of the present invention is to reduce the aforementioned technical problems of the prior-art by providing a new type of method and appa- ratus for depositing nanoparticles on a moveable line of flexible material.
  • the apparatus for roll-to-roll treating of a surface of a moveable line of flexible material comprises a first endless surface and a second endless surface, wherein the moveable line of flexible material may be taken up from the first endless surface and taken in onto the second endless surface at equal speed.
  • the apparatus also comprises means for treating the surface of the line of flexible material extending between the first endless surface and the second endless surface.
  • the means for treating the surface of the moveable line of flexible material is configured to deposit nanoparti- cles onto the moveable line of flexible material, wherein the means for treating the surface is arranged to generate the nanoparticles by an aerosol method.
  • the method for roll-to-roll treating of a surface of a line of flexible material comprises the step of moving the line of flexible material in between a first endless surface and a second endless surface by taking the flexible material up from the first endless surface and taking the flexible material in onto the second endless surface.
  • the method also comprises the steps of generating nanoparticles by an aerosol method and depositing the nanoparticles onto the line of flexible material .
  • An aerosol method is used for generating and depositing nanoparticles on a moveable line of flexible material in an apparatus for roll-to-roll treating of a surface of the moveable line of flexible material.
  • the apparatus comprises a first endless surface and a second endless surface.
  • the moveable line of flexible material may be taken up from the first endless surface and taken in onto the second endless surface at equal speed.
  • the apparatus comprises a means for spreading the flow of nanoparticles, wherein the means for spreading is in flow connection with the means for treating, for increasing the density of nanoparticles on the move- able line of flexible material.
  • the apparatus comprises two or more means for treating the surface of the line of flexible material, wherein the means for treating are positioned successively in the direction of movement of the moveable line of flexible material, for increasing the density of nanoparticles on the moveable line of flexible material.
  • density should be understood as meaning the number of particles per unit surface area.
  • the method comprises the step of treating the surface of the line of flexible material with two or more means for treating, wherein the means for treating are positioned successively in the direction of movement of the move- able line of flexible material, for increasing the density of nanoparticles on the moveable line of flexible material.
  • the apparatus comprises a means for rapidly moving the line of flexible material through a gaseous environment, for decreasing heating of the line of flexible material.
  • the method according to the present inven- tion comprises the step of decreasing heating of the line of flexible material by rapidly moving the line of flexible material through a gaseous environment.
  • An increased line speed also enables efficient extraction of heat from the line of flexible material.
  • This surprising effect can be used e.g. to cool down the roll-to-roll substrate after a section of it has been exposed to a hot flame of an LFS system. This reduces the potentially detrimental effects of excessive heat exposure on the roll-to-roll sub- strate and/or to the nanoparticle coating itself.
  • the means for treating the surface is arranged to generate the nanoparticles such that chemical reactions causing the formation of nanoparticles are enabled by a supply of thermal energy into aerosol.
  • the means for treating the surface is a thermal reactor, which generates the nanoparticles from gaseous and/or liquid precursors.
  • the method comprises the step of supplying thermal energy into aerosol to enable the formation of nanoparticles .
  • Thermal energy may be supplied into the aero- sol e.g. airborne liquid precursor droplets by means of e.g. a high temperature flame or an oven through which the precursor droplets and/or particles may be injected.
  • the supply of thermal energy enables and/or accelerates the dynamics of the chemical reactions leading to the formation of nanoparticles via gas phase reactions between the vaporized liquid precur- sors and with possibly other reagents.
  • the means for treating the surface is arranged to generate the nanoparticles by a liquid flame spray method.
  • the aerosol method is a liquid flame spray method.
  • the liquid flame spray method to generate nanoparticles may be implemented in a relatively simple apparatus without the need to use complicated vacuum equipment and is especially suitable for integra- tion to an apparatus for roll-to-roll coating.
  • the means for treating the surface comprises an inlet for feeding a liquid solution into the means for treating, wherein the liquid solution comprises pre- cursor required for the generation of nanoparticles.
  • the method comprises the step of adjusting the speed of the line of flexible material, in order to modify the properties of the coating of nanoparticles inde- pendently from the size of the nanoparticles. It has been observed that the size of nanoparticles in the coating of nanoparticles is essentially independent of the line speed of the flexible substrate used in the roll-to-roll coating process. This enables precise tailoring of the nanostructure of the coating by e.g. using the line speed of the substrate to adjust the density of nanoparticles in the coating while the parameters of the aerosol synthesis method can be used the modify the size of the deposited particles.
  • the method comprises the step of feeding liquid solution into a means for treating the surface, wherein the solution comprises all precursors required for the generation of nanoparticles .
  • the method comprises the step of feeding liquid solution into a means for treating the surface, wherein the solution comprises only one of the precursors required for the generation of nanoparticles.
  • the precursors used for generating the nanoparticles according to the present invention may be supplied into the means for treating the surface, e.g. into a spray head arranged to generate nanoparticles by the liquid flame spray method, as a liquid solution.
  • This liquid solution or mixture of many solutions may comprise all the precursors needed to gener- ate nanoparticles with a targeted composition.
  • the precursors may also be supplied separately into the means for treating the surface from their respective liquid solutions and even sprayed separately into air or into other heated space, e.g. a thermal reactor, where the nanoparticles are generated, so that a single droplet in the aerosol only contains one precursor .
  • the apparatus comprises a third endless surface for taking a line of lamination material up from the third endless surface and in onto the second endless surface at equal speed such that the coating of nanoparticles ends up in between the lamination material and the line of flexible material.
  • the method according to the present invention comprises the step of taking lamination material up from a third endless surface and taking the lamination material in onto the second endless surface such that the coating of nanoparticles ends up in between the lamination material and the line of flexible material.
  • the apparatus comprises means for extrusion coating the coating of nanoparticles with lamination material, wherein the lamination material is a polymer compound.
  • the method according to the present invention comprises the step of extrusion coating the coating of nanoparticles with a lamination material, wherein the lamination material is a polymer compound.
  • the apparatus is used for extrusion coating the coating of nanoparticles by means of the lamination material, wherein the lamination material is a polymer compound.
  • the apparatus comprises one or more spray heads side by side arranged in close proximity of the surface of the line of flexible material extended linearly be- tween the first endless surface and the second endless surface.
  • the one or more spray heads are arranged to spray the nanoparticles onto the surface of the line of flexible material such that the distribution of nanoparticles substantially covers the entire width of the line of flexible material.
  • the aforementioned placement of spray heads improves the productivity of the apparatus according to the present invention as a section of the moveable line of flexible material only has to pass once under the one or more spray heads to get essentially entirely coated with nanoparticles over its whole width.
  • the nanoparticles are deposited onto the surface of the line of flexible material using one or more spray heads such that the distribution of nanoparticles sub- stantially covers the entire width of the line of flexible material.
  • the apparatus comprises means for adjusting the take up speed of the first and/or the third endless surface and the take in speed of the second endless surface to adjust the line speed of the line of flexible material for controlling the density of nanoparticles on the flexible surface.
  • the method according to the present invention comprises the step of adjusting the take up speed of the first and/or the third endless surface and the take in speed of the second endless surface to adjust the line speed of the line of flexible material for controlling the density of nanoparticles on the flexible surface.
  • the apparatus comprises means for injecting droplets into a thermal reactor comprising one or more flames.
  • the apparatus comprises a spray head wherein the gases needed to generate the nanoparticles and the gases needed to generate the flame emerge to air through the same opening.
  • the nanoparticles are deposited onto the surface of the line of flexible material through a spray head wherein the gases needed to generate the nanoparticles and the gases needed to generate the flame emerge to air through the same opening.
  • the spray of nanoparticles may be more accurately directed as opposed to a design where the reagents for nanoparticle generation are injected to a flame at an angle.
  • the design of the spray head according to the present invention may also be simplified as there is no need for a separate means or opening for supplying the reagents into the high temperature flame.
  • the apparatus is used to coat the moveable line of flexible material selected from the group of paper, paperboard, aluminum, polymer, material containing paper, non-woven, fabric, filter cloth, glass fabric, glass cloth, woven glass, metal and ceramic.
  • the apparatus according to the present invention may be used to deposit nanoparticles on a flexible line of material comprising e.g. paper, paperboard, aluminum film, plastic or polymer film, extrusion coated substrates, laminates containing e.g. paper, paperboard, aluminum, plastic film, extrusion coated substrates, non woven, fabric, filter cloth and fab- ric, glass fabric or cloth, woven glass, metal and ceramic film or ceramic coated material.
  • the apparatus is used for depositing nanoparticles on the line of flexible material for controlling its wear resistance, abrasion resistance, thermal resistance, oxidation resistance, chemical resistance, UV- resistance, antibacterial properties, magnetic properties, hydrophobic properties, coefficient of friction, porosity, moisture barrier properties, oxygen barrier properties, gas barrier properties, grease barrier properties, adhesion properties, printing properties, heat seal properties and/or hot tack properties.
  • the present invention provides a cost- effective technique for high volume roll-to-roll coating of a flexible line of material with nanoparticles generated by an aerosol-based method.
  • An aerosol method or an aerosol-based method in this context may be understood as a method in which small liquid pre- cursor droplets are formed by injecting the liquid precursors through a spray head into air. These small droplets are then vaporized at least partially in air and the nanoparticles are generated via gas phase reactions between e.g. different species of precursor vapour and possibly other gas phase reactants such as oxygen .
  • the aerosol-based roll-to-roll apparatus used for coating according to the present invention is not material-specific.
  • the apparatus may be used to syn- thesize a variety of different materials, metals, semiconductors and insulators, in the form of nanoparticles by choosing the right precursor materials and other process parameters for a targeted material.
  • the coating of the flexible material according to the pre- sent invention does not require expensive and complicated vacuum technology but can be carried out in atmospheric conditions.
  • the embodiments of the invention described hereinbefore may be used in any combination with each other. Several of the embodiments may be combined together to form a further embodiment of the invention.
  • a method or an apparatus, to which the invention is related, may comprise at least one of the embodiments of the invention described hereinbefore.
  • Fig. 1 is a schematic illustration of a prior art spray head arrangement for an apparatus for a liq- uid atomization based flame method
  • Fig. 2 is a schematic side-view illustration of a roll-to-roll coating apparatus according to one embodiment of the present invention
  • Fig. 3 is a schematic side-view illustration of a roll-to-roll coating apparatus according to another embodiment of the present invention.
  • Fig. 4 is a schematic illustration of a spray head for a liquid flame spray apparatus of Fig. 3, according to one embodiment of the present invention
  • Fig. 5 is a schematic side-view illustration of a roll-to-roll coating apparatus according to another embodiment of the present invention
  • Fig. 6 is a three dimensional schematic illustration of a roll-to-roll coating apparatus with multiple spray heads, according to one embodiment of the present invention
  • Fig. 7 is a three dimensional schematic illustration of a roll-to-roll coating apparatus with three spray heads positioned successively in the di- rection of line movement, according to one embodiment of the present invention
  • Fig. 8 is a schematic side-view illustration of a roll-to-roll coating apparatus according to another embodiment of the present invention.
  • a prior-art spray head arrangement 1 of Fig. 1 for a liquid atomization based flame method comprises separately a head for generating a high- temperature flame 10 from combustion gases, the flame head 3, and a head for feeding reagent droplets 12 into the flame 10 to generate nanoparticles 11, the droplet head 4.
  • the spray head arrangement 1 further comprises an inlet for a first combustion gas 6, an inlet for a second combustion gas 7 and an inlet for the precursors (reagents) 8.
  • the reagents are injected to the high temperature flame 10 through the reagent inlet 8 and through the droplet head 4 from the reagent containers using a liquid pump.
  • the reagents are in liquid form and may be introduced to the droplet head 4 as a solution comprising all the required reagent components to synthesize the desired nanoparticles 11.
  • the reagents may also be introduced into the droplet head 4 as separate solutions for each reagent.
  • a nozzle at the end of the droplet head 4 forms small droplets 12 from the liquid reagents and feeds the droplets 12 towards the flame 10 at an angle with the stream of combustion gases. When the droplets 12 reach the flame 10 the high temperature of the flame 10 vaporizes the drop- lets 12 and increases the energy of the reagent molecules.
  • nanoparticles 11 are carried within the flame 10 in the stream of com- bustion gases and reaction by-products in a direction essentially away from the combustion head 3.
  • the apparatus of Fig. 2 comprises means for treating 5 the surface of a line 15 of flexible material.
  • the means for treating 5 is positioned over the moveable line 15 of flexible material and the nanoparticles 11 generated in or by the means for treating 5 impinge on the flexible material forming a coating 16 of nanoparticles 11.
  • the apparatus further comprises a first endless surface 17 and a second endless surface 18.
  • the first endless surface 17 and the second endless surface 18 may be e.g. cylinders or conveyor belts.
  • the flexible material to be coated is wrapped around the first endless surface 17 i.e. around e.g. the round surface of a cylinder.
  • the means for treat- ing 5 the surface of a line of flexible material may be any apparatus arranged to generate nanoparticles 11 by an aerosol-based method.
  • the means for treating 5 may be e.g. an oven in which the nanoparticles are generated from liquid precursor droplets or the spray head 5 of Fig. 4, a more detailed description of which will follow.
  • Droplets 12 can also be sprayed separately into a thermal reactor e.g. a flame 10.
  • the spray head 5 of Fig. 4 is positioned over a moveable line 15 of flexible material and the nanoparticles 11 generated in the spray head 5 impinge on the flexible material forming a coating 16 of nanoparticles 11.
  • the apparatus of Fig. 3 comprises the spray head 5, a first endless surface 17 and a second endless surface 18.
  • the spray head 5 additionally comprises separate inlets for a first liquid reagent 13 and for a second liquid reagent 14.
  • the first endless surface 17 and the second endless surface 18 may be e.g. cylinders or conveyor belts.
  • the flexible material to be coated is wrapped around the first endless surface 17 i.e. around e.g. the round surface of a cylinder. Before beginning the coating process the line
  • the line 15 of flexible material is attached to the second endless surface 18.
  • the second endless surface 18 is rotated with e.g. the power of an electrical motor the line 15 of flexible material is taken up from the first endless surface 17 and taken in onto the second endless surface 18.
  • This electrical motor may also be used to control the speed of the line 15 of flexible material and thereby the density of nanoparticles 11 to control e.g. the porosity of the coating 16 of nanoparticles 11 as described above.
  • a section of the moving line 15 of flexible material moves under a stream of nanoparticles 11 gen- erated in e.g. a spray head 5 with the liquid flame spray method or other aerosol-based method according to the present invention.
  • the nanoparticles 11 adhere to the surface of the line 15 of flexible material forming a coating 16 of nanoparticles 11 on the sur- face.
  • the flexible material may be e.g. cardboard, flexible packaging material, metal or nonwoven material depending on the targeted application.
  • the spray head 5 of the configuration 2 of Fig. 4 is the means for treating 5 the line 15 of flexible material as presented in the apparatus of Fig. 3 according to the present invention.
  • the spray head 5 of Fig. 4 comprises inlets for the liquid re- agents 9 and for a first combustion gas 6 and a second combustion gas 7.
  • the liquid reagent droplets 12 are sprayed in the air through the same nozzle as the combustion gases at the flame end of the spray head 5.
  • This type of spray head configuration 2 improves the control of the flow direction of nanoparticles 11 since the flow direction of reagents remains essentially constant in the flame 10.
  • the reagents are injected to the high tem- perature flame 10 through the spray head 5 from reagent containers using a liquid pump.
  • the reagents are in liquid form and may be introduced to the spray head 5 as a solution comprising all the required reagent components to synthesize the desired nanoparticles 11.
  • the reagents may also be introduced into the spray head 5 as separate solutions for each reagent.
  • a nozzle at the end of the spray head 5 forms small droplets 12 from the liquid reagents and feeds the droplets 12 in the flame 10 essentially in the direction of the combustion gases. When the droplets 12 reach the flame 10 the high temperature of the flame 10 vaporizes the droplets 12 and increases the energy of the reagent molecules.
  • Feasible precursors (reagents) to be used in liquid form to generate the nanoparticles 11 according to the present invention include e.g. metals in or- ganic or inorganic solvents, metal salts in organic or inorganic solvents and metal alkoxides in organic solvents.
  • the materials of generated nanoparticles 11 and the coating 16 of nanoparticles 11 include e.g. metal, metaloxide, composite of different metals, composite of oxides and metals and composite of different oxides .
  • the apparatus of Fig. 5 comprises a third endless surface 19 e.g. a rotatable cylinder or a conveyor belt which has lamination material 20 wrapped around it.
  • the lamination material 20 may be taken up from the third endless surface 19 and taken in onto the second endless surface 18.
  • the lamination material 20 wraps around the nanoparticle coating 16 on the line of 15 flexible material resulting in es- sentially a three layer structure.
  • the apparatus of Fig. 5 may be used in e.g. an extrusion coating process to improve the adhesion of the polymer film i.e. the lamination material 20 to the line 15 of flexible material e.g. cardboard.
  • the coating 16 of nanoparticles 11 acts as an adhesion layer.
  • the endless surfaces 17, 18, 19 in Fig. 2, Fig. 3, Fig. 5 and Fig. 6 are rotatable and the rotation speed naturally defines the speed of the line 15 of flexible material and the speed of the line of lamination material 20 which are equal so that the layered structure may be formed and wrapped around the second endless surface 18.
  • the apparatus of Fig. 5 also comprises means 21 for thermal treatment of the coated line of flexi- ble material.
  • the means 21 is placed at the other side of the line 15 of flexible material in Fig. 5, i.e. to the side opposite to the coated side, but the placement of the means 21 may vary according to the process.
  • Thermal treatment may also be applied to the line of lamination material 20.
  • the means 22 for thermal treatment of the line of lamination material 20 may be used e.g. for extrusion coating where the polymer lamination commonly requires a thermal treatment before the lamination step.
  • Fig. 6 presents how multiple spray heads may be placed in the apparatus according to the present invention to coat a line 15 of flexible material having a width much larger than the width of the nanopar- ticle 11 stream emerging from a single spray head 5 according to the present invention. Placing the spray heads 5 side by side perpendicularly to the direction of movement of the line to be coated a uniform coverage of nanoparticles 11 may be obtained essentially over the entire width of the line. This type of placement of the means for treatment may be utilized also in the thermal treatment of the lamination material 20 and/or the coated line 15 of flexible material.
  • the line speed of the substrate i.e. the line 15 of flexible material, and the parameters of the flame 10 are interrelated, and a suitable set of process parameters depends on the targeted end prod- uct, the coated line 15 of flexible material.
  • the line speed can however be adjusted to control the density of nanoparticles 11 independently of their size which is determined by the synthesis method, e.g. the LFS method.
  • density should be understood as meaning the number of particles per unit surface area .
  • a given size of nanoparticles 11 may therefore require that the flame 10 be located at a certain distance from the line 15 of flexible material and that the flame 10 be of a certain size and temperature.
  • the flame (s) may therefore heat the coating 16 and/or the substrate line 15.
  • the heating should be prevented or minimized.
  • One way of doing this is rapidly moving the line 15 of flexible material, to create a thin gaseous boundary layer over the line 15 of flexible material. This minimizes heat transfer from the flame 10, or from another heating apparatus, onto the line 15 of flexible material and/or onto the coating 16.
  • the density of deposited nanoparticles 11 in the coating 16 depends on the exposure time of a section of the line 15 to the flux of nanoparticles 11.
  • the apparatus of Fig. 7 comprises means 23 for rapidly moving the line 15 of flexible material. Three spray heads 5 are positioned over the line 15 successively in the direction of movement of the line 15 of flexible material. This successive positioning enables us- ing a higher line speed for the substrate compared to the apparatus of Fig. 3 with a given density per unit surface area of nanoparticles 11 in the nanoparticle coating 16. This results from an increased overall spread of the stream of nanoparticles 11 in the direc- tion of movement of the line 15, which can be used to keep the exposure time constant even if the line speed increases.
  • the spread of the stream of nanoparticles 11 in the direction of movement of the line 15 of flexible material can also be increased by other means and methods.
  • the spread of nanoparticles 11 can be increased by even a single means for treating 5 attached to a suitably designed nozzle (a means for spreading 24) which spreads the flow of nanoparticles 11 onto the surface of the line 15 of flexible material.
  • a suitably designed nozzle a means for spreading 24
  • an increased line speed efficiently decreases heating of the line 15 of flexible material. This is a result of the formation of a gaseous boundary layer over the line 15 of flexible mate- rial.
  • the formation mechanism of a boundary layer on a moving surface will be obvious for a skilled person.
  • the gaseous boundary layer slows down conduction and convection of heat from the source of thermal energy to the surface of the line 15 of flexible material.
  • An increased line speed also results in more efficient extraction of heat from the coated substrate line to the environment, which e.g. reduces the risk of combustion of the substrate as a result of the flame 10, or otherwise reduces the effects of heating on the coating 16 and/or on the line substrate.
  • This enables e.g. the use of thermally more sensitive coatings 16, or substrate materials for the line 15 of flexible material, such as filter, cloth, non-woven, fabric, textile, paper, various polymers or aluminum foil.
  • the apparatus of Fig. 7 is therefore especially suitable for roll-to-roll depositing on substrates which can be destroyed by heat emerging from e.g. the flames 10 or from other sources of thermal energy.
  • Nanoparticles 11 travel through this gaseous boundary layer 11 by e.g. diffusion before they are deposited on the substrate.
  • the spread of the flux of nanoparticles 11 in the direction of movement of the line 15 substrate can be adjusted by e.g. only using some of the spray heads 5 in the apparatus of Fig. 7 to synthesize and deposit the nanoparticles 11.
  • This apparatus therefore enables the adjustment of the line speed without affecting the density of nanoparticles 11 on the substrate, which brings a lot of flexibility to the roll-to-roll deposition process and to the possible substrate and coating materials.
  • a thermally sensitive substrate such as paper
  • the speed of the substrate line 15 may have to be kept high, e.g. at least 25 m per minute, not to cause burning of the paper under the flame (s) .
  • a high line speed decreases the exposure time of a section of the line to the flux of nanoparticles 11 and therefore the density of nanoparticles 11 on the substrate. Hence the coating may become too thin and/or too porous.
  • the exposure time of a section of the line to the flux of nanoparticles 11, and there- fore the density of nanoparticles 11 on the substrate can be maintained at increased line speeds using a more widely spread stream (or rather a sum of three individual streams emerging from their respective spray heads 5) of nanoparticles 11 in the direction of the line movement.
  • other properties may also be compensated for by the wider spread of the nanoparticle 11 stream from successive spray heads 5.
  • the line speed may also be modified to adjust the properties of the coating, often through modified thermal management, independently of the size of the nanoparticles 11.
  • the line speed can be increased to increase the ratio of the anatase phase to the rutile phase content in titania and/or to increase hydropho- bicity of the coating resulting from decreased oxygenation of the surface of the coating caused by re- symbolized heating.
  • the heat sealing properties of PE-LD may be improved by increasing the line speed.
  • the apparatus of Fig. 7 may also be used to fabricate layered structures by synthesizing nanopar- ticles 11 of different composition in the different spray heads 5.
  • the different layers may import differ- ent functionality to the coating; the layer closest to the substrate may for example flatten out the surface of the substrate or act as an adhesion layer, the second layer can serve the purpose of a moisture barrier, while the outermost layer is a protective coating.
  • the number of spray heads 5 successively positioned over the line 15 of flexible material, and the material which the individual spray heads 5 deposit, may vary depending on the specific application.

Abstract

An apparatus and a method for roll-to-roll treating of a surface of a moveable line (15) of flexible material. The apparatus comprises a first endless surface (17) and a second endless surface (18), wherein the moveable line (15) of flexible material may be taken up from the first endless surface (17) and taken in onto the second endless surface (18) at equal speed. The apparatus also comprises means for treating (5) the surface of the line of flexible material extending between the first endless surface (17) and the second endless surface (18). The means for treating (5) the surface of the moveable line (15) of flexible material is configured to deposit nanoparticles (11) onto the moveable line (15) of flexible material. The means for treating (5) the surface is arranged to generate the nanoparticles (11) by an aerosol method.

Description

ROLL-TO-ROLL METHOD AND APPARATUS FOR COATING A SURFACE
FIELD OF THE INVENTION The present invention relates to coating technology. Especially the present invention relates to a roll-to-roll method and apparatus for coating a flexible surface by nanoparticles .
BACKGROUND OF THE INVENTION
Nanosized particles i.e. nanoparticles may be generated using various different methods exploiting chemical compounds as precursors. These methods include sol-gel and electrochemical methods, which can be classified as liquid phase methods. Gas phase methods include e.g. plasma spray and flame spray pyroly- sis. Aerosol-based methods such as the liquid flame spray (LFS) method may be used to generate nanoparticles from liquid precursors which are injected as small droplets through a spray head into a flame generated by a highly exothermic combustion reaction utilizing combustion gases. Combustion gases in the LFS method may be e.g. hydrogen and oxygen. Also hydrocarbons may be used to produce a flame in which case the oxygen required for the combustion reaction to take place may be obtained from air. The small precursor droplets rapidly evaporate as they come into contact with the high temperature in the flame and react with possibly other evaporated precursors to pro- duce nanoparticles.
In LFS the chemical reactions occurring in the flame are rapid as the combustion reaction may increase the temperature inside the flame to up to about 2500 °C . The gas flow in the flame is commonly turbu- lent, which distributes the nanoparticles generated in the flame randomly in the gas flow. A coating made of nanoparticles on a surface may be formed by directing the gas flow and the nanoparticle stream onto the surface. LFS and other aerosol-based nanoparticle coating methods may be utilized on many different substrate materials to provide functionality on their surfaces or to otherwise modify the surface properties such as electrical conductivity or barrier properties against e.g. moisture.
Flame treatment is a known and widely used method for e.g. improving adhesion of plastic coating onto cardboard or paper in an extrusion coating process. The method can also be used e.g. to improve printability between plastic and ink or toner. In flame treatment methane or propane reacts with air and the flame generated by the combustion reaction oxidizes, dries and removes non-uniformities from the surface, which improves the adhesion properties of the surface. By treating a plastic surface with a high temperature flame the surface is oxidized and the en- ergy of the plastic surface may be increased, which improves the printability and the coatability of the surface .
Prior-art related to flame treatment and LFS methods have been disclosed in patents # US7220398 and # GB1026305. US7220398 discloses how liquid feed flame spray pyrolysis may be employed to generate mixed- metal oxide nanoparticles from a combustible liquid aerosol. GB1026305 discloses how flame or heat treatment may be employed to apply a thermoplastic coating on a line of material by separately spraying the powdered thermoplastic material on a moveable surface.
There exist many coating technologies that can be used to deposit a wide range of materials in a roll-to-roll concept, such as CVD, MOCVD, PECVD and ALD. The problem with these technologies is that they rely on complex vacuum technology. Furthermore the growth rate of film with these technologies is often relatively low. Both of these aforementioned aspects potentially limit the productivity and cost- effectiveness otherwise achievable with a roll-to-roll coating concept. The production scale coating of a flexible substrate material in a roll-to-roll configuration is commonly limited to the aforementioned technologies employing vacuum. Additionally the deposition of con- trollably porous coatings with the aforementioned vac- uum techniques is challenging as the film's growth mechanism in these techniques rely on nucleation of atoms or molecules on the surface of the substrate.
Although there exist atmospheric techniques for roll-to-roll production these techniques and the corresponding apparatuses are material-specific such as the one disclosed in GB1026305 which is not able to synthesize a wide spectrum of different materials from a variety precursors through chemical reactions forming nanoparticles .
PURPOSE OF THE INVENTION
The purpose of the present invention is to reduce the aforementioned technical problems of the prior-art by providing a new type of method and appa- ratus for depositing nanoparticles on a moveable line of flexible material.
SUMN[ARY OF THE INVENTION
The apparatus according to the present inven- tion is characterized by what is presented in independent claim 1.
The method according to the present invention is characterized by what is presented in independent claim 14. The use according to the present invention is characterized by what is presented in independent claim 27. The apparatus for roll-to-roll treating of a surface of a moveable line of flexible material according to the present invention comprises a first endless surface and a second endless surface, wherein the moveable line of flexible material may be taken up from the first endless surface and taken in onto the second endless surface at equal speed. The apparatus also comprises means for treating the surface of the line of flexible material extending between the first endless surface and the second endless surface. The means for treating the surface of the moveable line of flexible material is configured to deposit nanoparti- cles onto the moveable line of flexible material, wherein the means for treating the surface is arranged to generate the nanoparticles by an aerosol method.
The method for roll-to-roll treating of a surface of a line of flexible material according to the present invention comprises the step of moving the line of flexible material in between a first endless surface and a second endless surface by taking the flexible material up from the first endless surface and taking the flexible material in onto the second endless surface. The method also comprises the steps of generating nanoparticles by an aerosol method and depositing the nanoparticles onto the line of flexible material .
An aerosol method according to the present invention is used for generating and depositing nanoparticles on a moveable line of flexible material in an apparatus for roll-to-roll treating of a surface of the moveable line of flexible material. The apparatus comprises a first endless surface and a second endless surface. The moveable line of flexible material may be taken up from the first endless surface and taken in onto the second endless surface at equal speed. In one embodiment of the present invention the apparatus comprises a means for spreading the flow of nanoparticles, wherein the means for spreading is in flow connection with the means for treating, for increasing the density of nanoparticles on the move- able line of flexible material.
In one embodiment of the present invention the apparatus comprises two or more means for treating the surface of the line of flexible material, wherein the means for treating are positioned successively in the direction of movement of the moveable line of flexible material, for increasing the density of nanoparticles on the moveable line of flexible material. In this context density should be understood as meaning the number of particles per unit surface area. In one embodiment of the present invention the method comprises the step of treating the surface of the line of flexible material with two or more means for treating, wherein the means for treating are positioned successively in the direction of movement of the move- able line of flexible material, for increasing the density of nanoparticles on the moveable line of flexible material.
In another embodiment of the present inven- tion the apparatus comprises a means for rapidly moving the line of flexible material through a gaseous environment, for decreasing heating of the line of flexible material. In one embodiment of the present invention the method according to the present inven- tion comprises the step of decreasing heating of the line of flexible material by rapidly moving the line of flexible material through a gaseous environment.
By successively positioning two or more means for treating the line of flexible material (e.g. spray heads for the LFS method) over the line of flexible material the spread of a nanoparticle stream emerging from the means can be increased and correspondingly the density of nanoparticles on the moving line of flexible material also increases with a given line speed and with a given distance of the means from the surface of the line. This gives the opportunity to in- crease the line speed as opposed to situation where only one means for treating is used in the direction of line movement. Surprisingly, an increased line speed efficiently decreases heating of the substrate as a result of the formation of a gaseous boundary layer over the line of flexible material. The gaseous boundary layer slows down conduction and convection of heat from the source of thermal energy to the surface of the substrate. An increased line speed also enables efficient extraction of heat from the line of flexible material. This surprising effect can be used e.g. to cool down the roll-to-roll substrate after a section of it has been exposed to a hot flame of an LFS system. This reduces the potentially detrimental effects of excessive heat exposure on the roll-to-roll sub- strate and/or to the nanoparticle coating itself.
In one embodiment of the present invention the means for treating the surface is arranged to generate the nanoparticles such that chemical reactions causing the formation of nanoparticles are enabled by a supply of thermal energy into aerosol.
In one embodiment of the present invention the means for treating the surface is a thermal reactor, which generates the nanoparticles from gaseous and/or liquid precursors. In another embodiment of the present invention the method comprises the step of supplying thermal energy into aerosol to enable the formation of nanoparticles .
Thermal energy may be supplied into the aero- sol e.g. airborne liquid precursor droplets by means of e.g. a high temperature flame or an oven through which the precursor droplets and/or particles may be injected. The supply of thermal energy enables and/or accelerates the dynamics of the chemical reactions leading to the formation of nanoparticles via gas phase reactions between the vaporized liquid precur- sors and with possibly other reagents.
In one embodiment of the present invention the means for treating the surface is arranged to generate the nanoparticles by a liquid flame spray method. In another embodiment of the present invention the aerosol method is a liquid flame spray method.
The liquid flame spray method to generate nanoparticles may be implemented in a relatively simple apparatus without the need to use complicated vacuum equipment and is especially suitable for integra- tion to an apparatus for roll-to-roll coating.
In one embodiment of the present invention the means for treating the surface comprises an inlet for feeding a liquid solution into the means for treating, wherein the liquid solution comprises pre- cursor required for the generation of nanoparticles.
In one embodiment of the present invention the method comprises the step of adjusting the speed of the line of flexible material, in order to modify the properties of the coating of nanoparticles inde- pendently from the size of the nanoparticles. It has been observed that the size of nanoparticles in the coating of nanoparticles is essentially independent of the line speed of the flexible substrate used in the roll-to-roll coating process. This enables precise tailoring of the nanostructure of the coating by e.g. using the line speed of the substrate to adjust the density of nanoparticles in the coating while the parameters of the aerosol synthesis method can be used the modify the size of the deposited particles. In one embodiment of the present invention the method comprises the step of feeding liquid solution into a means for treating the surface, wherein the solution comprises all precursors required for the generation of nanoparticles .
In another embodiment of the present invention the method comprises the step of feeding liquid solution into a means for treating the surface, wherein the solution comprises only one of the precursors required for the generation of nanoparticles.
The precursors used for generating the nanoparticles according to the present invention may be supplied into the means for treating the surface, e.g. into a spray head arranged to generate nanoparticles by the liquid flame spray method, as a liquid solution. This liquid solution or mixture of many solutions may comprise all the precursors needed to gener- ate nanoparticles with a targeted composition. The precursors may also be supplied separately into the means for treating the surface from their respective liquid solutions and even sprayed separately into air or into other heated space, e.g. a thermal reactor, where the nanoparticles are generated, so that a single droplet in the aerosol only contains one precursor .
In one embodiment of the present invention the apparatus comprises a third endless surface for taking a line of lamination material up from the third endless surface and in onto the second endless surface at equal speed such that the coating of nanoparticles ends up in between the lamination material and the line of flexible material. In another embodiment of the present invention the method according to the present invention comprises the step of taking lamination material up from a third endless surface and taking the lamination material in onto the second endless surface such that the coating of nanoparticles ends up in between the lamination material and the line of flexible material. In one embodiment of the present invention the apparatus comprises means for extrusion coating the coating of nanoparticles with lamination material, wherein the lamination material is a polymer compound. In another embodiment of the present invention the method according to the present invention comprises the step of extrusion coating the coating of nanoparticles with a lamination material, wherein the lamination material is a polymer compound. In another embodiment of the present invention the apparatus is used for extrusion coating the coating of nanoparticles by means of the lamination material, wherein the lamination material is a polymer compound. By utilizing a coating of nanoparticles in between the line of flexible material and the lamination material, e.g. a polymer compound, the adhesion of the lamination material to the flexible material may be improved. This can be exploited in e.g. an ex- trusion coating process.
In one embodiment of the present invention the apparatus comprises one or more spray heads side by side arranged in close proximity of the surface of the line of flexible material extended linearly be- tween the first endless surface and the second endless surface. The one or more spray heads are arranged to spray the nanoparticles onto the surface of the line of flexible material such that the distribution of nanoparticles substantially covers the entire width of the line of flexible material. The aforementioned placement of spray heads improves the productivity of the apparatus according to the present invention as a section of the moveable line of flexible material only has to pass once under the one or more spray heads to get essentially entirely coated with nanoparticles over its whole width. In one embodiment of the present invention the nanoparticles are deposited onto the surface of the line of flexible material using one or more spray heads such that the distribution of nanoparticles sub- stantially covers the entire width of the line of flexible material.
In one embodiment of the present invention the apparatus comprises means for adjusting the take up speed of the first and/or the third endless surface and the take in speed of the second endless surface to adjust the line speed of the line of flexible material for controlling the density of nanoparticles on the flexible surface.
In another embodiment of the present inven- tion the method according to the present invention comprises the step of adjusting the take up speed of the first and/or the third endless surface and the take in speed of the second endless surface to adjust the line speed of the line of flexible material for controlling the density of nanoparticles on the flexible surface.
When other process parameters are kept constant and a continuous spray of nanoparticles is directed onto the moveable line of flexible material us- ing a higher line speed reduces the density of nanoparticles on the line of flexible material. This results from the fact that the residence time of a line section under the continuous spray of nanoparticles decreases. Correspondingly the density of nanoparticles may be increased by decreasing the line speed. By adjusting the density of nanoparticles in the coating on the line of flexible material many properties of the coating may be controlled. E.g. the porosity of the coating may be increased by using a smaller density of nanoparticles. The porosity of the coating on the other hand may affect e.g. the hyro- philicity of the coating. In one embodiment of the present invention the apparatus comprises means for injecting droplets into a thermal reactor comprising one or more flames.
In one embodiment of the present invention the apparatus comprises a spray head wherein the gases needed to generate the nanoparticles and the gases needed to generate the flame emerge to air through the same opening.
In another embodiment of the present inven- tion the nanoparticles are deposited onto the surface of the line of flexible material through a spray head wherein the gases needed to generate the nanoparticles and the gases needed to generate the flame emerge to air through the same opening. When the gas mixtures needed for combustion and nanoparticle generation are ejected to air through the same opening the spray of nanoparticles may be more accurately directed as opposed to a design where the reagents for nanoparticle generation are injected to a flame at an angle. The design of the spray head according to the present invention may also be simplified as there is no need for a separate means or opening for supplying the reagents into the high temperature flame. In one embodiment of the present invention the apparatus is used to coat the moveable line of flexible material selected from the group of paper, paperboard, aluminum, polymer, material containing paper, non-woven, fabric, filter cloth, glass fabric, glass cloth, woven glass, metal and ceramic. In general the apparatus according to the present invention may be used to deposit nanoparticles on a flexible line of material comprising e.g. paper, paperboard, aluminum film, plastic or polymer film, extrusion coated substrates, laminates containing e.g. paper, paperboard, aluminum, plastic film, extrusion coated substrates, non woven, fabric, filter cloth and fab- ric, glass fabric or cloth, woven glass, metal and ceramic film or ceramic coated material.
In one embodiment of the present invention the apparatus is used for depositing nanoparticles on the line of flexible material for controlling its wear resistance, abrasion resistance, thermal resistance, oxidation resistance, chemical resistance, UV- resistance, antibacterial properties, magnetic properties, hydrophobic properties, coefficient of friction, porosity, moisture barrier properties, oxygen barrier properties, gas barrier properties, grease barrier properties, adhesion properties, printing properties, heat seal properties and/or hot tack properties.
The present invention provides a cost- effective technique for high volume roll-to-roll coating of a flexible line of material with nanoparticles generated by an aerosol-based method. An aerosol method or an aerosol-based method in this context may be understood as a method in which small liquid pre- cursor droplets are formed by injecting the liquid precursors through a spray head into air. These small droplets are then vaporized at least partially in air and the nanoparticles are generated via gas phase reactions between e.g. different species of precursor vapour and possibly other gas phase reactants such as oxygen .
The aerosol-based roll-to-roll apparatus used for coating according to the present invention is not material-specific. The apparatus may be used to syn- thesize a variety of different materials, metals, semiconductors and insulators, in the form of nanoparticles by choosing the right precursor materials and other process parameters for a targeted material. The coating of the flexible material according to the pre- sent invention does not require expensive and complicated vacuum technology but can be carried out in atmospheric conditions. The embodiments of the invention described hereinbefore may be used in any combination with each other. Several of the embodiments may be combined together to form a further embodiment of the invention. A method or an apparatus, to which the invention is related, may comprise at least one of the embodiments of the invention described hereinbefore.
DETAILED DESCRIPTION OF THE INVENTION In the following, the present invention will be described in more detail with references to the accompanying figures, in which
Fig. 1 is a schematic illustration of a prior art spray head arrangement for an apparatus for a liq- uid atomization based flame method,
Fig. 2 is a schematic side-view illustration of a roll-to-roll coating apparatus according to one embodiment of the present invention,
Fig. 3 is a schematic side-view illustration of a roll-to-roll coating apparatus according to another embodiment of the present invention,
Fig. 4 is a schematic illustration of a spray head for a liquid flame spray apparatus of Fig. 3, according to one embodiment of the present invention, Fig. 5 is a schematic side-view illustration of a roll-to-roll coating apparatus according to another embodiment of the present invention,
Fig. 6 is a three dimensional schematic illustration of a roll-to-roll coating apparatus with multiple spray heads, according to one embodiment of the present invention,
Fig. 7 is a three dimensional schematic illustration of a roll-to-roll coating apparatus with three spray heads positioned successively in the di- rection of line movement, according to one embodiment of the present invention, and Fig. 8 is a schematic side-view illustration of a roll-to-roll coating apparatus according to another embodiment of the present invention.
For reasons of simplicity, item numbers will be maintained in the following exemplary embodiments in the case of repeating components.
A prior-art spray head arrangement 1 of Fig. 1 for a liquid atomization based flame method, comprises separately a head for generating a high- temperature flame 10 from combustion gases, the flame head 3, and a head for feeding reagent droplets 12 into the flame 10 to generate nanoparticles 11, the droplet head 4. The spray head arrangement 1 further comprises an inlet for a first combustion gas 6, an inlet for a second combustion gas 7 and an inlet for the precursors (reagents) 8.
There exist many different chemistries to generate the flame 10 by combustion in the liquid flame spray method and in liquid atomization based flame methods in general. E.g. oxygen, hydrogen and/or hydrocarbons may be fed into the inlets 6, 7 of the flame head 3 and ignited by e.g. a spark outside the flame head 3. In the case of hydrocarbons the oxygen needed for the combustion reaction may be acquired from air. When the combustion gases are ignited, the flame 10 can be maintained by a continuous supply of the combustion gases into the flame 10.
The reagents are injected to the high temperature flame 10 through the reagent inlet 8 and through the droplet head 4 from the reagent containers using a liquid pump. The reagents are in liquid form and may be introduced to the droplet head 4 as a solution comprising all the required reagent components to synthesize the desired nanoparticles 11. The reagents may also be introduced into the droplet head 4 as separate solutions for each reagent. A nozzle at the end of the droplet head 4 forms small droplets 12 from the liquid reagents and feeds the droplets 12 towards the flame 10 at an angle with the stream of combustion gases. When the droplets 12 reach the flame 10 the high temperature of the flame 10 vaporizes the drop- lets 12 and increases the energy of the reagent molecules. This enables the different reagents to react with each other in the gas phase resulting in the formation of nanosized particles. These nanoparticles 11 are carried within the flame 10 in the stream of com- bustion gases and reaction by-products in a direction essentially away from the combustion head 3.
The apparatus of Fig. 2 comprises means for treating 5 the surface of a line 15 of flexible material. The means for treating 5 is positioned over the moveable line 15 of flexible material and the nanoparticles 11 generated in or by the means for treating 5 impinge on the flexible material forming a coating 16 of nanoparticles 11. The apparatus further comprises a first endless surface 17 and a second endless surface 18. The first endless surface 17 and the second endless surface 18 may be e.g. cylinders or conveyor belts. The flexible material to be coated is wrapped around the first endless surface 17 i.e. around e.g. the round surface of a cylinder. The means for treat- ing 5 the surface of a line of flexible material may be any apparatus arranged to generate nanoparticles 11 by an aerosol-based method. The means for treating 5 may be e.g. an oven in which the nanoparticles are generated from liquid precursor droplets or the spray head 5 of Fig. 4, a more detailed description of which will follow. Droplets 12 can also be sprayed separately into a thermal reactor e.g. a flame 10.
In Fig. 3 the spray head 5 of Fig. 4 is positioned over a moveable line 15 of flexible material and the nanoparticles 11 generated in the spray head 5 impinge on the flexible material forming a coating 16 of nanoparticles 11. The apparatus of Fig. 3 comprises the spray head 5, a first endless surface 17 and a second endless surface 18. The spray head 5 additionally comprises separate inlets for a first liquid reagent 13 and for a second liquid reagent 14. The first endless surface 17 and the second endless surface 18 may be e.g. cylinders or conveyor belts. The flexible material to be coated is wrapped around the first endless surface 17 i.e. around e.g. the round surface of a cylinder. Before beginning the coating process the line
15 of flexible material is attached to the second endless surface 18. When the second endless surface 18 is rotated with e.g. the power of an electrical motor the line 15 of flexible material is taken up from the first endless surface 17 and taken in onto the second endless surface 18. This electrical motor may also be used to control the speed of the line 15 of flexible material and thereby the density of nanoparticles 11 to control e.g. the porosity of the coating 16 of nanoparticles 11 as described above.
After the uptake from the first endless surface 17 and before the intake onto the second endless surface 18 a section of the moving line 15 of flexible material moves under a stream of nanoparticles 11 gen- erated in e.g. a spray head 5 with the liquid flame spray method or other aerosol-based method according to the present invention. The nanoparticles 11 adhere to the surface of the line 15 of flexible material forming a coating 16 of nanoparticles 11 on the sur- face. The flexible material may be e.g. cardboard, flexible packaging material, metal or nonwoven material depending on the targeted application.
The spray head 5 of the configuration 2 of Fig. 4 is the means for treating 5 the line 15 of flexible material as presented in the apparatus of Fig. 3 according to the present invention. The spray head 5 of Fig. 4 comprises inlets for the liquid re- agents 9 and for a first combustion gas 6 and a second combustion gas 7. The liquid reagent droplets 12 are sprayed in the air through the same nozzle as the combustion gases at the flame end of the spray head 5. This type of spray head configuration 2 improves the control of the flow direction of nanoparticles 11 since the flow direction of reagents remains essentially constant in the flame 10.
The reagents are injected to the high tem- perature flame 10 through the spray head 5 from reagent containers using a liquid pump. The reagents are in liquid form and may be introduced to the spray head 5 as a solution comprising all the required reagent components to synthesize the desired nanoparticles 11. The reagents may also be introduced into the spray head 5 as separate solutions for each reagent. A nozzle at the end of the spray head 5 forms small droplets 12 from the liquid reagents and feeds the droplets 12 in the flame 10 essentially in the direction of the combustion gases. When the droplets 12 reach the flame 10 the high temperature of the flame 10 vaporizes the droplets 12 and increases the energy of the reagent molecules. This enables the different reagents to react with each other in the gas phase re- suiting in the formation of nanosized particles 11. Thermal energy can also be supplied to the reagent molecules by burning solvent in the precursor droplets 12. The nanoparticles 11 are carried within the flame 10 in the stream of combustion gases and reaction by- products in a direction essentially away from the spray head 5.
Feasible precursors (reagents) to be used in liquid form to generate the nanoparticles 11 according to the present invention include e.g. metals in or- ganic or inorganic solvents, metal salts in organic or inorganic solvents and metal alkoxides in organic solvents. The materials of generated nanoparticles 11 and the coating 16 of nanoparticles 11 include e.g. metal, metaloxide, composite of different metals, composite of oxides and metals and composite of different oxides . The apparatus of Fig. 5 comprises a third endless surface 19 e.g. a rotatable cylinder or a conveyor belt which has lamination material 20 wrapped around it. In a similar fashion as the line 15 of flexible material the lamination material 20 may be taken up from the third endless surface 19 and taken in onto the second endless surface 18. When the lamination material 20 is taken in onto the second endless surface 18 it wraps around the nanoparticle coating 16 on the line of 15 flexible material resulting in es- sentially a three layer structure. The apparatus of Fig. 5 may be used in e.g. an extrusion coating process to improve the adhesion of the polymer film i.e. the lamination material 20 to the line 15 of flexible material e.g. cardboard. In this case the coating 16 of nanoparticles 11 acts as an adhesion layer.
The endless surfaces 17, 18, 19 in Fig. 2, Fig. 3, Fig. 5 and Fig. 6 are rotatable and the rotation speed naturally defines the speed of the line 15 of flexible material and the speed of the line of lamination material 20 which are equal so that the layered structure may be formed and wrapped around the second endless surface 18.
The apparatus of Fig. 5 also comprises means 21 for thermal treatment of the coated line of flexi- ble material. The means 21 is placed at the other side of the line 15 of flexible material in Fig. 5, i.e. to the side opposite to the coated side, but the placement of the means 21 may vary according to the process. Thermal treatment may also be applied to the line of lamination material 20. The means 22 for thermal treatment of the line of lamination material 20 may be used e.g. for extrusion coating where the polymer lamination commonly requires a thermal treatment before the lamination step.
Fig. 6 presents how multiple spray heads may be placed in the apparatus according to the present invention to coat a line 15 of flexible material having a width much larger than the width of the nanopar- ticle 11 stream emerging from a single spray head 5 according to the present invention. Placing the spray heads 5 side by side perpendicularly to the direction of movement of the line to be coated a uniform coverage of nanoparticles 11 may be obtained essentially over the entire width of the line. This type of placement of the means for treatment may be utilized also in the thermal treatment of the lamination material 20 and/or the coated line 15 of flexible material.
The line speed of the substrate, i.e. the line 15 of flexible material, and the parameters of the flame 10 are interrelated, and a suitable set of process parameters depends on the targeted end prod- uct, the coated line 15 of flexible material. The line speed can however be adjusted to control the density of nanoparticles 11 independently of their size which is determined by the synthesis method, e.g. the LFS method. In this context density should be understood as meaning the number of particles per unit surface area .
The parameters affecting the size of the nanoparticles 11, the "flame parameters", include the temperature of the flame 10, the distance of the flame 10 from the moving target substrate, and the "size" of the flame 10 which, on the other hand, depends on e.g. reagents and combustion gases, and the rate with which the reagents and the combustion gases are injected into air out from the spray head 5. A given size of nanoparticles 11 may therefore require that the flame 10 be located at a certain distance from the line 15 of flexible material and that the flame 10 be of a certain size and temperature. The flame (s) may therefore heat the coating 16 and/or the substrate line 15. As many flexible substrates materials and/or coatings 16 are thermally not very stable the heating should be prevented or minimized. One way of doing this is rapidly moving the line 15 of flexible material, to create a thin gaseous boundary layer over the line 15 of flexible material. This minimizes heat transfer from the flame 10, or from another heating apparatus, onto the line 15 of flexible material and/or onto the coating 16.
The density of deposited nanoparticles 11 in the coating 16 depends on the exposure time of a section of the line 15 to the flux of nanoparticles 11. The apparatus of Fig. 7 comprises means 23 for rapidly moving the line 15 of flexible material. Three spray heads 5 are positioned over the line 15 successively in the direction of movement of the line 15 of flexible material. This successive positioning enables us- ing a higher line speed for the substrate compared to the apparatus of Fig. 3 with a given density per unit surface area of nanoparticles 11 in the nanoparticle coating 16. This results from an increased overall spread of the stream of nanoparticles 11 in the direc- tion of movement of the line 15, which can be used to keep the exposure time constant even if the line speed increases. In addition to the successive positioning of two or more spray heads 5, the spread of the stream of nanoparticles 11 in the direction of movement of the line 15 of flexible material can also be increased by other means and methods. In another embodiment of the invention, as presented in Fig. 8, the spread of nanoparticles 11 can be increased by even a single means for treating 5 attached to a suitably designed nozzle (a means for spreading 24) which spreads the flow of nanoparticles 11 onto the surface of the line 15 of flexible material. Surprisingly, an increased line speed efficiently decreases heating of the line 15 of flexible material. This is a result of the formation of a gaseous boundary layer over the line 15 of flexible mate- rial. The formation mechanism of a boundary layer on a moving surface will be obvious for a skilled person. The gaseous boundary layer slows down conduction and convection of heat from the source of thermal energy to the surface of the line 15 of flexible material. An increased line speed also results in more efficient extraction of heat from the coated substrate line to the environment, which e.g. reduces the risk of combustion of the substrate as a result of the flame 10, or otherwise reduces the effects of heating on the coating 16 and/or on the line substrate. This enables e.g. the use of thermally more sensitive coatings 16, or substrate materials for the line 15 of flexible material, such as filter, cloth, non-woven, fabric, textile, paper, various polymers or aluminum foil. The apparatus of Fig. 7 is therefore especially suitable for roll-to-roll depositing on substrates which can be destroyed by heat emerging from e.g. the flames 10 or from other sources of thermal energy.
An additional benefit of increased line speed is a more uniform distribution of nanoparticles 11 on the moving substrate as a result of the formation of the thin boundary layer over the substrate at high line speeds. Nanoparticles 11 travel through this gaseous boundary layer 11 by e.g. diffusion before they are deposited on the substrate.
The spread of the flux of nanoparticles 11 in the direction of movement of the line 15 substrate can be adjusted by e.g. only using some of the spray heads 5 in the apparatus of Fig. 7 to synthesize and deposit the nanoparticles 11. This apparatus therefore enables the adjustment of the line speed without affecting the density of nanoparticles 11 on the substrate, which brings a lot of flexibility to the roll-to-roll deposition process and to the possible substrate and coating materials. If a thermally sensitive substrate, such as paper, is to be coated with nanoparticles 11 of a certain size, the speed of the substrate line 15 may have to be kept high, e.g. at least 25 m per minute, not to cause burning of the paper under the flame (s) . A high line speed, on the other hand, decreases the exposure time of a section of the line to the flux of nanoparticles 11 and therefore the density of nanoparticles 11 on the substrate. Hence the coating may become too thin and/or too porous. With the apparatus of Fig. 7 the exposure time of a section of the line to the flux of nanoparticles 11, and there- fore the density of nanoparticles 11 on the substrate can be maintained at increased line speeds using a more widely spread stream (or rather a sum of three individual streams emerging from their respective spray heads 5) of nanoparticles 11 in the direction of the line movement. Analogously to the effect of modified line speed on the density of nanoparticles 11, other properties may also be compensated for by the wider spread of the nanoparticle 11 stream from successive spray heads 5. In addition to efficiently decreasing heating of the moving line 15 of flexible material the line speed may also be modified to adjust the properties of the coating, often through modified thermal management, independently of the size of the nanoparticles 11. For example the line speed can be increased to increase the ratio of the anatase phase to the rutile phase content in titania and/or to increase hydropho- bicity of the coating resulting from decreased oxygenation of the surface of the coating caused by re- duced heating. Similarly the heat sealing properties of PE-LD may be improved by increasing the line speed. The apparatus of Fig. 7 may also be used to fabricate layered structures by synthesizing nanopar- ticles 11 of different composition in the different spray heads 5. The different layers may import differ- ent functionality to the coating; the layer closest to the substrate may for example flatten out the surface of the substrate or act as an adhesion layer, the second layer can serve the purpose of a moisture barrier, while the outermost layer is a protective coating. The number of spray heads 5 successively positioned over the line 15 of flexible material, and the material which the individual spray heads 5 deposit, may vary depending on the specific application. These possible additional embodiments of the invention are limited only by the scope of the claims.
The directions of gas flow, particle flow, line movement and rotation of the endless surfaces 17, 18, 19 are indicated by arrows in the figures.
As is clear for a person skilled in the art, the invention is not limited to the examples described above but the embodiments can freely vary within the scope of the claims.

Claims

1. An apparatus for roll-to-roll treating of a surface of a moveable line (15) of flexible material, the apparatus comprising a first endless surface (17) and a second endless surface (18), wherein the moveable line (15) of flexible material may be taken up from the first endless (17) surface and taken in onto the second endless surface (18), and means for treating (5) the surface of the line of flexible mate- rial extending between the first endless surface (17) and the second endless surface (18) , characteri zed in that the means for treating (5) the surface of the moveable line (15) of flexible material is configured to deposit nanoparticles (11) onto the move- able line (15) of flexible material, wherein the means for treating (5) the surface is arranged to generate the nanoparticles (11) by an aerosol method.
2. The apparatus of claim 1, characteri zed in that the apparatus comprises a means for spreading (24) the flow of nanoparticles (11), wherein the means for spreading (24) is in flow connection with the means for treating (5), for increasing the density of nanoparticles (11) on the moveable line
(15) of flexible material.
3. The apparatus of any one of claims 1 - 2, characterized in that the apparatus comprises two or more means for treating (5) the surface of the line (15) of flexible material, wherein the means for treating (5) are positioned successively in the direc- tion of movement of the moveable line (15) of flexible material, for increasing the density of nanoparticles (11) on the moveable line (15) of flexible material.
4. The apparatus of any one of claims 1 - 3, characteri zed in that the apparatus comprises a means (23) for rapidly moving the line (15) of flexible material through a gaseous environment, for decreasing heating of the line (15) of flexible material .
5. The apparatus of any one of claims 1 - 4, characteri zed in that the means for treating (5) the surface is arranged to generate the nanoparti- cles (11) such that chemical reactions causing the formation of nanoparticles are enabled by a supply of thermal energy into aerosol.
6. The apparatus of any one of claims 1 - 5, characteri zed in that the means for treating
(5) the surface is a thermal reactor, which generates the nanoparticles (11) from gaseous and/or liquid precursors .
7. The apparatus of any one of claims 1 - 6, characteri zed in that the means for treating
(5) the surface is arranged to generate the nanoparticles (11) by a liquid flame spray method.
8. The apparatus of any one of claims 1 - 7, characteri zed in that the means for treating (5) the surface comprises an inlet for feeding a liquid solution into the means for treating (5), wherein the liquid solution comprises precursor required for the generation of nanoparticles (11).
9. The apparatus of any one of claims 1 - 8, characteri zed in that the apparatus comprises a third endless surface (19) for taking a line of lamination material (20) up from the third endless surface (19) and in onto the second endless (18) surface at equal speed such that the coating (16) of nanoparticles (11) ends up in between the lamination material (20) and the line (15) of flexible material.
10. The apparatus of any one of claims claim 1 - 9, characteri zed in that the apparatus comprises means for extrusion coating the coating (16) of nanoparticles (11) with lamination material (20), wherein the lamination material (20) is a polymer compound.
11. The apparatus of any one of claims 1 -
10, characteri zed in that the apparatus comprises one or more spray heads (5) side by side arranged in close proximity of the surface of the line (15) of flexible material extended linearly between the first endless surface (17) and the second endless surface (18), wherein the one or more spray heads (5) are arranged to spray the nanoparticles (11) onto the surface of the line (15) of flexible material such that the distribution of nanoparticles (11) substantially covers the entire width of the line (15) of flexible material.
12. The apparatus of any one of claims 1 -
11, characteri zed in that the apparatus com- prises means for adjusting the take up speed of the first (17) and/or the third (19) endless surface and the take in speed of the second (18) endless surface to adjust the line speed of the line (15) of flexible material for controlling the density of nanoparticles (11) on the flexible surface.
13. The apparatus of any one of claims 1 -
12, characteri zed in that the means for treating the surface of the line (15) of flexible material comprises a spray head (5) wherein the gases needed to generate the nanoparticles (11) and the gases needed to generate the flame (10) emerge to air through the same opening.
14. A method for roll-to-roll treating of a surface of a line (15) of flexible material, wherein the method comprises the step of moving the line (15) of flexible material in between a first endless surface (17) and a second endless surface (18) by taking the flexible material up from the first endless surface (17) and taking the flexible material in onto the second endless surface (18) , characteri zed in that the method comprises the steps of generating nanoparticles (11) by an aerosol method and depositing the nanoparticles (11) onto the line (15) of flexible material.
15. The method of claim 14, characteri zed in that the method comprises the step of treating the surface of the line (15) of flexible material with two or more means (5) , wherein the means for treating (5) are positioned successively in the direction of movement of the moveable line (15) of flexible material, for increasing the density of nanoparticles (11) on the move- able line (15) of flexible material.
16. The method of any one of claims 14 - 15, characteri zed in that the method comprises the step of adjusting the speed of the line (15) of flexible material, in order to modify the properties of the coating (16) of nanoparticles (11) independently from the size of the nanoparticles (11).
17. The method of any one of claims 14 - 16, characteri zed in that the method comprises the step of decreasing heating of the line (15) of flexible material by rapidly moving the line (15) of flexible material through a gaseous environment.
18. The method of any one of claims 14 - 17, characteri zed in that the method comprises the step of supplying thermal energy into aerosol to enable the formation of nanoparticles (11).
19. The method of any one of claims 14 - 18, characteri zed in that the aerosol method is a liquid flame spray method.
20. The method of any one of claims 14 - 19, characteri zed in that the method comprises the step of feeding liquid solution into a means for treating (5) the surface, wherein the solution comprises all precursors required for the generation of nanoparticles (11).
21. The method of any one of claims 14 - 19, characteri zed in that the method comprises the step of feeding liquid solution into a means for treating (5) the surface, wherein the solution comprises only one of the precursors required for the generation of nanoparticles (11).
22. The method of any one of claims 14 - 21, characteri zed in that the method comprises the step of taking lamination material (20) up from a third endless surface (19) and taking the lamination material (20) in onto the second endless surface (18) such that the coating (16) of nanoparticles (11) ends up in between the lamination material (20) and the line (15) of flexible material.
23. The method of any one of claims 14 - 22, characteri zed in that the method comprises the step of extrusion coating the coating (16) of nanoparticles (11) with lamination material (20), wherein the lamination material (20) is a polymer compound.
24. The method of any one of claims 14 - 23, characteri zed in that the nanoparticles (11) are deposited onto the surface of the line (15) of flexible material using one or more spray heads (5) such that the distribution of nanoparticles (11) sub- stantially covers the entire width of the line (15) of flexible material.
25. The method of any one of claims 14 - 24, characteri zed in that the method comprises the step of adjusting the take up speed of the first (17) and/or the third (19) endless surface and the take in speed of the second endless surface (18) to adjust the line speed of the line (15) of flexible material for controlling the density of nanoparticles (11) on the flexible surface.
26. The method of any one of claims 14 - 25, characteri zed in that the nanoparticles (11) are deposited onto the flexible material through a spray head (5) wherein the gases needed to generate the nanoparticles (11) and the gases needed to generate the flame (10) emerge to air through the same opening.
27. Use of an aerosol method for generating and depositing nanoparticles (11) on a moveable line (15) of flexible material in an apparatus for roll-to- roll treating of a surface of the moveable line (15) of flexible material, the apparatus comprising a first endless surface (17) and a second endless surface (18), wherein the moveable line (15) of flexible material may be taken up from the first endless surface (17) and taken in onto the second endless surface (18) at equal speed.
28. The use of claim 27, characteri zed in that the aerosol method is a liquid flame spray method.
29. The use of any one of claims 27 - 28, characteri zed in that the apparatus is used to coat the moveable line (15) of flexible material selected from the group of paper, paperboard, aluminum, polymer, material containing paper, non-woven, fabric, filter cloth, glass fabric, glass cloth, woven glass, metal and ceramic.
30. The use of any one of claims 27 - 29, characteri zed in that the apparatus is used for extrusion coating the coating (16) of nanoparti- cles (11) by means of lamination material (20), wherein the lamination material (20) is a polymer compound.
31. The use of any one of claims 27 - 30, characteri zed in that the apparatus is used for depositing nanoparticles (11) on the line (15) of flexible material for controlling its wear resistance, abrasion resistance, thermal resistance, oxidation resistance, chemical resistance, UV-resistance, antibac- terial properties, magnetic properties, hydrophobic properties, coefficient of friction, porosity, moisture barrier properties, oxygen barrier properties, gas barrier properties, grease barrier properties, adhesion properties, printing properties, heat seal properties and/or hot tack properties.
PCT/FI2009/050084 2008-01-31 2009-01-30 Roll-to-roll method and apparatus for coating a surface WO2009095545A1 (en)

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WO2011073508A1 (en) * 2009-12-15 2011-06-23 Beneq Oy Process and apparatus for producing a substrate

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US5665277A (en) * 1994-10-27 1997-09-09 Northwestern University Nanoparticle synthesis apparatus and method
EP0955642A2 (en) * 1998-04-29 1999-11-10 Morton International, Inc. Formation of thin films resistors
EP1669747A1 (en) * 2004-12-09 2006-06-14 ETH Zürich Formation of highly porous gas-sensing layers by deposition of nanoparticles produced by flame spray pyrolysis
WO2006099156A2 (en) * 2005-03-10 2006-09-21 Tailored Materials Corporation Thin film production method and apparatus

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US5665277A (en) * 1994-10-27 1997-09-09 Northwestern University Nanoparticle synthesis apparatus and method
EP0955642A2 (en) * 1998-04-29 1999-11-10 Morton International, Inc. Formation of thin films resistors
EP1669747A1 (en) * 2004-12-09 2006-06-14 ETH Zürich Formation of highly porous gas-sensing layers by deposition of nanoparticles produced by flame spray pyrolysis
WO2006099156A2 (en) * 2005-03-10 2006-09-21 Tailored Materials Corporation Thin film production method and apparatus

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011073508A1 (en) * 2009-12-15 2011-06-23 Beneq Oy Process and apparatus for producing a substrate

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