Coated wood products and method of producing coated wood products

Information

  • Patent Grant
  • 11045798
  • Patent Number
    11,045,798
  • Date Filed
    Thursday, June 21, 2012
    12 years ago
  • Date Issued
    Tuesday, June 29, 2021
    3 years ago
Abstract
A coated wood product, comprising a barrier layer and a photocatalytic layer and a method for producing such a coated wood product.
Description
TECHNICAL FIELD

The disclosure generally relates to the field of wood products, e.g. building panels, such as floor panels, with a surface of wood. The disclosure more particularly relates to a building panel with coated surface of wood.


BACKGROUND

For a lacquered solid wood floor the visual appearance is very important. Furthermore, due to new regulations it is important to introduce properties that can reduce the level of indoor volatile organic compounds (VOC's).


It is well known that building materials can obtain photocatalytic properties. U.S. Pat. No. 6,409,821 describes how to apply TiO2 to external cement building materials by mixing micron sized TiO2 in the bulk cement mixture. Furthermore, it was shown in WO 2009/062516 that it is possible to apply nanoparticles on a laminate surface or on an overlay paper and introduce photocatalytic properties to internal surfaces.


US 2010/0058954 describes a carbon-modified titanium dioxide film arranged on a substrate such as glass, metal, plastic or titanium dioxide film. A barrier layer may be arranged to prevent potential diffusion of sodium and other ions from the substrate into the carbon-modified titanium dioxide film. The photocatalytic activity can be inhibited by diffusion of sodium and other ions from the substrate.


OBJECTS OF THE INVENTION

An objective of at least certain embodiments of the present invention is to provide a lacquered or varnished board or panel such as a lacquered solid wood flooring having improved washing properties thereby providing an overall cleaner looking floor.


An objective of at least certain embodiments of the present invention is to provide a lacquered or varnished board or panel such as a lacquered solid wood flooring having improved VOC removing properties thereby providing an overall better indoor environment.


Still another objective of at least certain embodiments is to provide a photocatalytic lacquered or varnished board or panel having an improved antimicrobial effect and/or an improved deodorizing effect and/or an improved degradation of VOC effect and/or anti stain properties of said lacquered or varnished board or panel.


Another objective of at least certain embodiments is to provide a lacquered board or panel having improved wash properties and/or VOC effect obtained by a transparent photocatalytic coating composition.


A further objective of at least certain embodiments is to provide a lacquered board or panel having improved wash properties and/or VOC effect and wherein these properties are durable and maintained under use conditions.


A still further objective of at least certain embodiments is to provide photocatalytic nanoparticle compositions suitable for functionalization of lacquered boards or panels. Said formulations may provide said functions more effectively and/or allow for use of less material and/or be more durable and/or be cheaper and/or allow for easier processing and/or processing at lower temperatures and/or allow for use under other illumination conditions than hitherto.


A still further objective of at least certain embodiments is to provide a transparent active photocatalytic composition on lacquered boards or panels with minimal impact on the underlying lacquer or varnish.


A still further objective of at least certain embodiments is to provide a transparent active photocatalytic composition on lacquered boards or panels with minimal impact on the underlying lacquer or varnish but still being active enough to provide improved VOC properties and/or washing properties at indoor light conditions.


A still further objective of at least certain embodiments is to provide transparent coating compositions to lacquered boards or panels without impacting the visual appearance of said lacquered boards or panels.


A still further objective of at least certain embodiments may be to provide transparent coating compositions to lacquered boards or panels without impacting the mechanical properties of said lacquered boards or panels.


A still further objective of at least certain embodiments is to provide water borne coating compositions to lacquered boards or panels maintaining the visual and mechanical properties of said lacquered boards or panels.


Furthermore, it can be an objective of at least certain embodiments of the present invention to provide a method for producing such photocatalytic lacquered boards or panels.


SUMMARY OF THE INVENTION

The present invention presents a method of introducing visible light sensitive and/or UV sensitive photocatalytic particles into lacquered boards or panels without damaging the underlying lacquer still maintaining a product capable of VOC reduction of indoor air. The present invention may comprise the step of spraying a photocatalytic coating composition into the top lacquer and drying and/or curing said photocatalytic composition. The present invention relates to a method of introducing said photocatalytic coating composition without altering the visual and mechanical properties of said lacquered boards or panels.


Furthermore, the present invention relates to a photocatalytic lacquered board or panel comprising a barrier layer, preferably transparent, and a photocatalytic composition layer, preferably transparent. The present product maintains the appearance and mechanical properties of the lacquered board or panel but also obtains a photocatalytic VOC reducing property.


A first aspect of the invention is a building panel comprising a surface of wood provided with a base coat, e.g. lacquer layer, and a topcoat, comprising barrier particles and photocatalytic nanoparticles. Preferably the barrier particles are embedded and substantially homogenously distributed in said topcoat. Preferably the photocatalytic nanoparticles are embedded and substantially homogenously distributed in said topcoat. In an alternative embodiment, the topcoat may also comprise a first layer, a barrier layer comprising said barrier particles, and a second layer of photocatalytic nanoparticles. Preferably the barrier particles are embedded and substantially homogenously distributed in said barrier layer. Preferably the photocatalytic nanoparticles are embedded and substantially homogenously distributed in said second layer. Between the first and the second layers there may be an area of mixed barrier and photocatalytic nanoparticles.


The topcoat may be transparent. The base coat may be at least one lacquer layer. The base coat may comprise more than one lacquer layer.


The barrier particles may be adapted to protect the base coat from the photocatalytic activity of the photocatalytic nanoparticles.


The barrier layer preferably comprises a silicium containing compound such as SiO2, colloidal SiO2, functional nanoscaled SiO2, silicone resin, organofunctional silanes, and/or colloidal silicic acid silane and/or a combination of said compounds.


The building panel, e.g. a floor panel, with the surface of wood may be a solid wood product, a panel for a parquet floor or engineered floor, a plywood or an HDF or MDF board provided with veneer or linoleum. Linoleum comprises wood material in form of wood flour or sawdust or cork.


A second coat may also be provided above the base coat and under the topcoat.


A layer may be arranged between the surface of wood and the base coat. Such a layer may be a print, a print layer or paint.


The inventive building panel can be provided with considerably improved washing properties. Specifically, when washing such a board or panel, water drops are spreading on the surface in such a manner that dirt is easier to suspend and remove without excessive use of special cleaning agents and harsh chemicals. The building panel thereby shows hydrophilic properties. Further drying is significantly faster and more uniform as water dries up substantially as a film instead of as contracting droplets and due to the larger surface area for evaporation. The more uniform drying process further results in that dried up water stains from dirt or dissolved salts in the water are avoided or considerably reduced as they are more evenly distributed on the surface. Thereby an overall cleaner looking board or panel after cleaning are provided.


Furthermore, the photocatalytic nanoparticles have VOC reducing properties. Thereby, the building panel reduces the level of indoor VOCs.


The barrier particles prevent the photocatalytic nanoparticles from make contact and react with the base coat, i.e. any underlying lacquer layer. If the photocatalytic nanoparticles react with the base coat or any other underlying lacquer layer, the base coat or any other underlying lacquer layer can be damaged by the photocatalytic activity of the nanoparticles. For example, the photocatalytic activity of the photocatalytic nanoparticles may degrade the base coat. The photocatalytic nanoparticles may impact properties of the base coat, such as changing the colour of the base coat.


A second aspect of the invention is a method of manufacturing a photocatalytic lacquered wood product comprising transparent photocatalytic nanoparticles, the method comprising the steps of:

    • applying a base coat by lacquering an underlying wood product to obtain at least one overlaying lacquer;
    • coating said overlying lacquer(s) with a barrier coating fluid, to obtain a transparent barrier layer;
    • coating said transparent barrier layer with a photocatalytic coating fluid, preferably comprising TiO2, to obtain a transparent photocatalytic layer; and
    • curing said overlaying lacquer(s), barrier layer and/or photocatalytic layer.


      The coating composition may be applied in one or more steps with optional step(s):
    • curing or semi-curing said barrier layer and/or overlying lacquer prior coating with a photocatalytic coating fluid;
    • drying said barrier coating fluid; and/or
    • drying said photocatalytic coating fluid


      The coating is preferably performed by spraying.


The photocatalytic coating fluid may comprise photocatalytic nanoparticles, preferably comprising TiO2. The concentration of said nanoparticles may be up to about 30 wt %, 20, wt %, 10 wt %, 5 wt % or 1 wt %.


The method may comprise a step between the coating step(s) and the curing step in which step(s) the excess solvent is evaporated/partly dried. By applying the barrier layer and/or photocatalytic nanoparticles in a wet surface the distribution of the particles is improved.


The barrier layer comprises preferably a silicium containing compound such as SiO2, colloidal SiO2, functional nanoscaled SiO2, silicone resin, organofunctional silanes, and/or colloidal silicic acid silane and/or a combination of said compounds.


Preferably, the barrier coating fluid and/or the photocatalytic coating fluid composition comprises a solvent comprising water. It is also contemplated that a solvent other than water is used.


The photocatalytic coating composition may comprise photocatalytic nanoparticles and a solvent, said solvent being selected from water, ethylene glycol, butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol or methoxypropanol or combinations thereof.


A third aspect of the invention is a building panel according to the first aspect produced by the method according the second aspect.


In embodiments of any aspects of the present invention the concentration of said nanoparticles in said coating fluids may be up to about 30 wt %, 20, wt %, 10 wt %, 5 wt %, or 1 wt %.


In embodiments of any aspects of the present invention the solid content in said barrier coating fluid may be up to about 30 wt %, 20, wt %, 10 wt %, 5 wt %, or 1 wt %.


In embodiments of any aspects of the invention the thickness of said barrier layer may be up to about 1 μm, 0.800 μm, 0.600 μm, 0.400 μm, 0.200 μm, 0.100 μm or 0.05 μm.


In embodiments of any aspects of the present invention, the thickness of said photocatalytic layer may up to about 1 μm, 0.800 μm, 0.600 μm, 0.400 μm, 0.200 μm, 0.100 μm or 0.05 μm.


In embodiments of any aspects of the present invention, the amount of said barrier and/or photocatalytic coating fluid(s) may be up to about 15 ml/m2, 10 ml/m2, 5 ml/m2 or 1 ml/m2.


In embodiments of any aspects of the present invention, said barrier and/or photocatalytic coating fluid(s) may be waterborne coating fluids.


In embodiments of any aspects of the present invention, said barrier and/or photocatalytic coating fluid(s) may be applied by spraying and the size of the droplet may be up to about 200 μm, 150 μm, 100 μm, 50 μm, 25 μm or 10 μm.


In embodiments of any aspects of the present invention, the photocatalytic particles may be visible light sensitive and/or UV sensitive photocatalytic particles.





BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure will in the following be described in connection to exemplary embodiments and in greater detail with reference to the appended exemplary drawings, wherein:



FIG. 1 Illustrates a wood product according to an embodiment of the invention;



FIG. 2 Illustrates a wood product according to an embodiment of the invention;



FIG. 3 Illustrates a method for producing a coated wood product;





DETAILED DESCRIPTION

In FIG. 1 an embodiment of a wood product 1, e.g. a photocatalytic lacquered board, is disclosed comprising a board 2 with a surface of wood, e.g. plywood, solid wood or a HDF/MDF board with a veneer or linoleum, a base coat 3 and a topcoat 5, 6. The topcoat comprises a barrier layer 5, comprising embedded barrier particles, and a second layer 6, comprising embedded photocatalytic nanoparticles. An area of mixed barrier and photocatalytic nanoparticles may be arranged between the barrier layer 5 and the second layer 6.


In an alternative embodiment, which is shown in FIG. 2, the topcoat 7 comprises barrier particles and photocatalytic nanoparticles. The topcoat 7 comprises a lower part with high concentration of the barrier particles and an upper part with a high concentration of the nanoparticles and a mixed area there between comprising both barrier particles and nanoparticles.


In one embodiment there is a second coat 4 above the base coat and under the topcoat. The second coat may be an additional lacquer layer. Also the base coat and the topcoat may comprise more than one layer in all embodiments.


In all embodiments, the base coat 3 may be at least one lacquer layer. By lacquer layer is also meant any varnish layer. The base coat 3 may be transparent. The base coat may for example be a UV curable lacquer or an oxidation lacquer (drying). The base coat is not part of a paper layer, as in a paper laminate. For example, the base layer may be a separate layer, independently applied to a topmost surface of a board.


Furthermore, in all embodiments, the topcoat 5, 6, 7 may be transparent. The topcoat may be a water-based coating or a solvent based coating. In an embodiment wherein the topcoat comprises a barrier layer 5 and a second layer 6 comprising the photocatalytic nanoparticles, both the barrier layer 5 and the second layer 6 may be transparent. The barrier layer is not part of a paper layer, as in a wear resistant layer in a paper laminate. For example, the barrier layer is a separate layer, independently applied to a base coat.


In all embodiments, the barrier particles are preferably SiO2, or a silicium containing compound such as SiO2, colloidal SiO2, functional nanoscaled SiO2, silicone resin, organofunctional silanes, and/or colloidal silicic acid silane and/or a combination of said compounds. The barrier particles protect the base coat from being damaged or impacted by the photocatalytic activity of the photocatalytic nanoparticles. The barrier particles prevent the base coat from being degraded by the photocatalytic activity of the photocatalytic nanoparticles.


The photocatalytic nanoparticles may be transparent. The photocatalytic nanoparticles may have a size of less than 35 nanometres, preferably about 20 nanometres.



FIG. 3 discloses a production line for manufacturing a photocatalytic lacquered wood product comprising transparent photocatalytic nanoparticles, the method comprising the steps of:

    • applying a base coat by lacquering on an underlying wood product to obtain at least one overlaying lacquer (step 31);
    • coating said overlaying lacquer(s) with a barrier coating fluid, preferably comprising a Si-containing compound, to obtain a transparent barrier layer (step 33);
    • coating said transparent barrier layer with a photocatalytic coating fluid, preferably comprising TiO2, to obtain a transparent photocatalytic layer (step 35); and
    • curing said overlaying lacquer(s), barrier layer and photocatalytic layer (step 37).


The production line may comprise one or more of the additional step(s):

    • Curing or semi-curing said overlaying lacquer, prior to coating with a barrier coating fluid (step 32);
    • drying said transparent barrier layer composition (step 34); and/or
    • drying said photocatalytic coating composition (step 36).


The coating is preferably performed by spraying.


Any step may be multiplied such as applying several layers of barrier/photocatalytic to obtain multi-layered products with longer service life.


The base coat may comprise more than one overlaying lacquer, for example a base lacquer, a middle lacquer and a top lacquer. The overlaying lacquer(s) may be for example be a UV curable lacquer or an oxidation lacquer (drying). The overlaying lacquer(s) may be transparent.


Example 1
Applying a Photocatalytic Top Layer Composition by Spray Application on Wet Top Lacquer—Air Mixed Nozzles

A 8×30 cm wooden floor board was lacquered with a base lacquer, a middle lacquer and a top lacquer forming overlying lacquers. The wet top lacquered wooden floor board entered the application of the photocatalytic composition coating with a velocity of 30 m/min. The wet lacquered wooden floor board was coated according to:

    • 1) 5 ml/m2 of a 5.6 wt % SiO2 in water fluid was applied.
    • 2) IR drying of the excess amount of water by a 3 kW IR lamp and by applying heated dry air.
    • 3) 5 ml/m2 of a 5.0 wt % TiO2 in water fluid was applied.
    • 4) IR drying of the excess amount of water by a 3 kW IR lamp and by applying heated dry air.
    • 5) Curing of the wooden composite sample with UV light.


Ad 1) The barrier layer coating fluid (1) used was a stable nanoparticle dispersion based on a 5.6 wt % water based dispersion of colloidal SiO2 surface modified with epoxy silane mixed with 0.5 wt % BYK 348 or similar as wetting agent. The average particle size was 7 nm. The barrier layer coating fluid was applied with air atomized nozzles (5 mL/m2 corresponding to 34 ml/min) given a droplet size of <50 micron meter average droplet size.


Ad 2) The barrier layer coated sample was IR dried with a 3 kW IR heating unit theoretically capable of evaporating 3-5 g/m2 of water.


Ad 3) The photocatalytic coating fluid (3) used was a stable TiO2 nanoparticle dispersion based on a 5.0 wt % water based dispersion of doped TiO2 capable of absorbing visible light (380-500 nm) mixed with 0.5 wt % BYK 348 as wetting agent. The average particle size was 18 nm. The photocatalytic coating fluid was applied with air atomized nozzles (5 mL/m2 corresponding to 34 ml/min) given a droplet size of <50 micron meter average droplet size.


Ad 4) The photocatalytic coated sample was IR dried with a 3 kW IR heating unit theoretically capable of evaporating 3-5 g/m2 of water.


Ad 5) The photocatalytic lacquered wooden sample was UV cured.


Example 1a
Applying a Photocatalytic Top Layer Composition by Spray Application on Wet Top Lacquer—Rotation Atomizer

Same as Example 1; however, the application of barrier layer (1) and the application of TiO2 (3) is made with a high speed rotating atomizer nozzle yielding a very fine mist of droplets making a very uniform coating.


Example 2
Photocatalytic Activity by EtOH Degradation

The photocatalytic activity of a sample prepared according to Example 1 was evaluated against degradation of EtOH by monitoring the CO2 release. The CO2 release test resulting from degradation of EtOH is a fast model experiment which is used to estimate the air quality improvement. The samples are placed in a 6 l sealed box with a 500 ppm ethanol atmosphere inside and the CO2 concentration is followed over time. The EtOH is degraded to CO2 due to the photocatalytic particles in the lacquered wood. The sample was irradiated with a light source yielding UV=1.250 mW/cm2.









TABLE 1







Activity of background substrated lacquered sample.









Photocatalytic Lacquer Sample














Rate [ppm CO2/hr]
25










Example 3
Improved Washability by Contact Angle Measurement

The contact angle with water was measured for a reference (no light) and for a photocatalytic coated sample as described in Example 1 applying the PGX from FIBRO System AB (see Table 2). These measurements were repeated 5 times at random positions on the board. Upon light exposure (0.68 W/m2/nm at 340 nm) the coated part of the lacquered board had become hydrophilic, as evidenced by the low contact angle. Importantly the photocatalytic topcoating was transparent making it invisible on the lacquered board. Furthermore, no chalking or other damaging effects of the lacquer were seen.









TABLE 2







Contact angle measurements.










Photocatalytic Lacquer
Reference













 0 hr
81.0 ± 3.0
79.8 ± 3.2


12 hr
65.2 ± 5.4
81.7 ± 0.8


61 hr
45.3 ± 3.6
76.7 ± 1.1


95 hr
48.5 ± 3.1
73.6 ± 1.0









Example 4
Applying a Photocatalytic Top Layer Composition by Spray Application on Wet Top Lacquer—Air Mixed Nozzles

A wooden floor board was lacquered with a base lacquer, a middle lacquer and a top UV curable lacquer forming overlying lacquers. The wet top lacquered wooden floor board entered the application of the photocatalytic composition coating with a velocity of 10 m/min. The wet lacquered wooden floor board was coated according to:

    • 1) 5 ml/m2 of an appr. 3.5 wt % aqueous solution of colloidal silicic acid silane fluid was applied.
    • 2) IR drying of the excess amount of water by 3 kW IR lamp and by applying forced heated dry air.
    • 3) 5 ml/m2 of a 1.0 wt % TiO2 in water fluid was applied.
    • 4) IR drying of the excess amount of water by 3 kW IR lamp and by applying forced heated dry air.
    • 5) Curing of the wooden composite sample with UV light.


Ad 1) The barrier layer coating fluid (1) used was an appr. 3.5 wt % aqueous solution of colloidal silicic acid silane fluid mixed with 0.5 wt % wetting agent. The barrier layer coating fluid was applied with air atomized nozzles (5 mL/m2 corresponding to 12.5 ml/min) given a droplet size of <50 micron meter average droplet size.


Ad 2) The barrier layer coated sample was IR dried with a 3 kW IR heating unit capable of evaporating 5 g/m2 of water.


Ad 3) The photocatalytic coating fluid (3) used was a stable TiO2 nanoparticle dispersion based on a 1.0 wt % water based dispersion of doped TiO2 capable of absorbing visible light (380-500 nm) mixed with 0.5 wt % wetting agent. The average particle size was 18 nm. The photocatalytic coating fluid was applied with air atomized nozzles (5 mL/m2 corresponding to 12.5 ml/min) given a droplet size of <50 micron meter average droplet size.


Ad 4) The photocatalytic coated sample was IR dried with a 3 kW IR heating unit capable of evaporating 3-5 g/m2 of water.


Ad 5) The photocatalytic lacquered wooden sample was UV cured.


Example 5
Visual Appearance and Gloss Level

The gloss level for a reference (no barrier layer and no photocatalytic particles) and for a photocatalytic coated sample as described in Example 4 were measured at an angle of 60°. These measurements were repeated 3 times at random positions on the board. Visual inspection of the photocatalytic coating showed a transparent coating on the lacquered board.









TABLE 3







Gloss measurements.










Photocatalytic Board
Reference Board







42.7 ± 1.1
38.8 ± 0.4









Claims
  • 1. A method of manufacturing a photocatalytic lacquered wood product, wherein the method comprises: lacquering an underlying wood product to obtain a base coat comprising at least one lacquer layer;coating said base coat with a barrier coating fluid comprising barrier particles, to obtain a transparent barrier layer;spraying said transparent barrier layer with a photocatalytic coating fluid comprising photocatalytic nanoparticles to obtain a transparent photocatalytic layer disposed on said transparent barrier layer, said photocatalytic nanoparticles being embedded and homogenously distributed in said transparent photocatalytic layer; and thencuring said wood product such that at least the base coat is cured.
  • 2. The method as claimed in claim 1, wherein the method comprises semi-curing said base coat, prior to coating with the barrier coating fluid.
  • 3. The method as claimed in claim 1, wherein the photocatalytic nanoparticles comprise TiO2.
  • 4. The method as claimed in claim 1, wherein a thickness of said barrier layer is up to about 1 μm.
  • 5. The method as claimed in claim 1, wherein a thickness of said photocatalytic layer is up to about 1 μm.
  • 6. A building panel produced according to the method in claim 1.
  • 7. The method as claimed in claim 1, further comprising curing the barrier layer.
  • 8. The method as claimed in claim 1, further comprising curing the photocatalytic layer.
  • 9. The method as claimed in claim 1, further comprising curing the barrier layer and the photocatalytic layer.
  • 10. The method as claimed in claim 1, wherein the base coat comprises a base lacquer, a middle lacquer and a top lacquer.
  • 11. The method as claimed in claim 1, wherein the barrier particles in the transparent barrier layer prevent the photocatalytic nanoparticles from reacting with the base coat.
  • 12. The method as claimed in claim 1, wherein a size of a droplet of the photocatalytic coating fluids is up to about 200 μm.
  • 13. The method as claimed in claim 1, wherein the method comprises drying said barrier coating fluid, prior to spraying with said photocatalytic coating fluid.
  • 14. The method as claimed in claim 13, wherein the barrier coating fluid is a waterborne fluid.
  • 15. The method as claimed in claim 13, wherein the barrier coating fluid is applied by spraying.
  • 16. The method as claimed in claim 15, wherein a size of a droplet of said barrier coating fluid is up to about 200 μm.
  • 17. The method as claimed in claim 1, further comprising drying said photocatalytic coating fluid after spraying said transparent barrier layer with said photocatalytic coating fluid and before said curing.
  • 18. The method as claimed in claim 1, wherein the photocatalytic coating fluid comprises the photocatalytic nanoparticles in a concentration of up to about 30 wt %.
  • 19. The method as claimed in claim 17, wherein an amount of at least one of said barrier or photocatalytic coating fluid(s) is up to about 15 ml/m2.
  • 20. The method as claimed in claim 17, wherein the photocatalytic coating fluid is a waterborne fluid.
  • 21. The method as claimed in claim 1, wherein the barrier particles comprise a silicon containing compound.
  • 22. The method as claimed in claim 21, wherein the silicon containing compound is selected from SiO2, colloidal SiO2, functional nanoscaled SiO2, silicone resin, organofunctional silanes, and/or colloidal silicic acid silane and/or a combination of said compounds.
CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of US. Provisional Application No. 61/504,558, filed on 5 Jul. 2011, and Swedish Application No. 1150636-7, filed on 5 Jul. 2011. The entire contents of each of U.S. Provisional Application No. 61/504,558, and Swedish Application No. 1150636-7 are hereby incorporated herein by reference in their entirety.

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Related Publications (1)
Number Date Country
20130011684 A1 Jan 2013 US
Provisional Applications (1)
Number Date Country
61504558 Jul 2011 US