Patent Application
20180257256
The present invention relates to a method for the treatment of wood material for protection against UV exposure and weathering as well as a wood material with resistance to UV exposure and weathering.
Wood is an excellent and widely used sustainable material for various applications such as construction and furniture, but it is prone to degradation under UV exposure. UV degradation leads to colour changes, surface alterations, and even to the destruction of wood material in presence of water, which strongly affects the reliability of wood in various applications.
Among the chemical components comprised in wood material, the highly branched phenolic polymer lignin is the best UV absorber in comparison to hemicellulose and cellulose. As a result, UV light in the solar spectrum can induce lignin degradation via photo-oxidation. The natural polymers undergo bond cleavage and hydrogen abstraction resulting in the formation of radicals or peroxides which finally decompose and generate the coloured and hydrophilic by-products (chromophores). Lignin is fragmented into low molecular weight species (such as water soluble polyphenols), which are washed away with the flow of water in outdoor applications. This exposes the underlying structure and leads to a degraded surface, which is more prone to fungal attack. In consequence, the photochemical reactions induced by UV radiation result in a significant surface alteration of wood such as loss of gloss and surface roughening, affecting its aesthetic appeal. Hence, there has been a widespread interest in preventing the photo-degradation of wood.
In the prior art different techniques to protect wood materials are known, which include chemical modification of the wood polymers, surface treatment with additives (organic and inorganic UV absorbers, radical scavengers), and finishing (varnishes and opaque coatings). Chemical modification of wood was typically carried out by bonding chemicals to the cell wall polymers that stabilize the colour of wood, such as acetylation and silylation. However, acetylated wood exhibited a colour stabilization effect only for 28 days, thereafter, the stabilization effect steadily diminishes and discoloration starts (Hon et al., Wood Fiber Sci. 27, 360-367; 1995). Silylation, thermal and copper ethanolamine treatment also caused the colour changing of wood specimens inevitably (Deka, M. et al. Wood Sci. Technol. 42, 5-20, 2008). Moreover, the photo degradation and leaching out of the organic molecules from the modified wood can be harmful to the environment and make the application of wood materials unsustainable. Wood surface coatings with inorganic nanoparticles as UV absorbers have the main drawback of leaching of added particles over time, lowering the protection efficiency, and necessitating regular application of new layers. In an attempt to overcome this limitation, a mix of inorganic UV absorbers and a clear organic coating to obtain highly durable and efficient UV protection coating was tested. ZnO-based acrylate coatings were applied to reduce yellowing under UV exposure. However, the self-degradation of the applied polymers limits their long-term performance in photo-stabilizing wood. In-situ coating of the substrate with a semiconductor layer via a liquid route, which has been developed by chemists for solar cell or transparent conductive electrodes, is emerging as a facile and promising method for wood UV protection. However, a ZnO nanorod array with a strong scattering effect to visible light diminishes the aesthetic appearance of wood surfaces. More importantly, the low crystalline coating exhibits poor durability under weathering conditions.
Here the inventors disclose a ZnO or titania based treatment method for protection of wood against UV as well as to achieve water repellent wood surfaces. The novelty of this invention is an in-situ treatment method to treat the rough wood surface (uneven topography with cut-open cells) with titania or ZnO nanorod arrays or a continuous film in the assistance of capping agents without exceeding temperature of 120° C. in case of ZnO or 200° C. in case of titania at any step. By further modifying the surface layer with hydrophobic molecules, a super-hydrophobic wood surface with low water drop adhesion can be achieved.
The problem underlying the present invention is to provide the means for a durable treatment of wood materials to increase their photostability and weathering resistance using an environmentally friendly, easy to use, and economic method. This problem is solved by the subject-matter of the independent claims.
The finding was made that titania or ZnO nanorod arrays or continuous films deposited onto the surface and/or within the first cell layer of wood material yield a UV-stable wood surface. The natural appearance of the surface of the wood material is preserved after treatment.
Furthermore, the UV-stable wood material can be further protected against the influence of environmental factors by deposition of thin SiO2 blocking layers onto the surface of ZnO nanorod arrays or continuous films in a conformational manner. This treatment also stabilizes hydrophobic molecules that may be introduced to the surface against a photo catalytic effect of ZnO in the presence of UV light.
Additionally, the ZnO treated wood material with or without the SiO2 treatment might be treated with hydrophobic molecules to yield a UV-stable and super-hydrophobic wood surface with low water drop adhesion.
The disclosed invention is a treatment of wood materials comprised of titania or ZnO nanorod arrays or a continuous film and hydrophobic molecules obtained by an in-situ coating method. This UV-stable and super-hydrophobic wood treatment with low water drop adhesion is obtained without exceeding temperatures of 120° C. in case of ZnO or 200° C. in case of titania at any step of the process. The presented method can be easily scaled-up for large scale surface modification.
According to a first aspect of the invention a method for treatment of wood material comprising a first and in some cases a second treatment step is provided. The first treatment step comprises the steps of provision of a first solution, immersion of the wood material into the first solution and drying of the wood material. In case of a second treatment step this step comprises the steps of provision of a second solution, immersion of the wood material into the second solution and drying of the wood material.
According to a second aspect of the invention a wood material is provided that is characterized by its resistance to UV exposure and weathering.
According to a third aspect of the invention a wood material obtainable by a process according to the first aspect of the invention is provided
The first aspect of the invention relates to a method for treatment of wood material that comprises a first and in some cases a second treatment step. In the first treatment step a first solution comprising zinc oxide in an aqueous solution or titanium(IV) isopropoxide (TTIP; CAS No: 546-68-9) in an organic solvent, in particular an alcohol, more particular ethanol, is provided. The wood material is immersed in the first solution and afterwards transferred to an oven suitable for drying of the wood material.
If not specified differently a drying step is not necessarily at a temperature over room temperature. A drying for a certain time in air is also possible.
In case that the first solution comprises zinc oxide the method additionally comprises a second treatment step. In the second treatment step a second solution comprising a zinc compound is provided and the wood material obtained by the first treatment step is immersed in the second solution and dried afterwards.
In the context of the present specification the term coating relates to depositions on the surface of materials as well as depositions on the surface that additionally penetrate into the upper layers of the material.
One sub aspect of the first aspect of the invention relates to a method for treatment of wood material that comprises provision of a first solution comprising zinc oxide.
A method for treatment of wood material comprising
is provided.
In certain embodiments, the first solution comprising zinc oxide has a pH>7, in particular a pH 8-14, more particular a pH 9-13, most particular pH 10 to 12.
In certain embodiments, the first solution has a pH of around 11, particular pH 11.
In certain embodiments, the second solution has a pH≥7, in particular a pH 7-14, more particular a pH 8-13, most particular pH 10 to 12.
In certain embodiments, the second solution has a pH of around 11.4, particular 11.4.
In certain embodiments, the first solution comprising zinc oxide has a pH>7, in particular a pH 8-14, more particular a pH 9-13, most particular pH 10 to 12 and the second solution has a pH≥7, in particular a pH 7-14, more particular a pH 8-13, most particular pH 10 to 12.
In certain embodiments, the first solution has a pH of around 11, particular pH 11 and the second solution has a pH of around 11.4, particular 11.4.
In certain embodiments, the first solution comprises zinc oxide with a concentration of 30 to 60 mM ZnO, particularly 40 to 55 mM ZnO, more particularly 40 to 50 mM ZnO and most particularly 50 mM ZnO.
In the context of the present specification the term percentage by weight (wt %) refers to the ratio of the mass of one substance to the mass of the total mixture multiplied by 100. Percentage by weight is calculated according to formula:
with ms being the mass of one substance in a mixture and mtot the mass of the total mixture.
In certain embodiments, in the first treatment step the wood material is immersed into the first solution comprising zinc oxide for 30 seconds up to 5 minutes, particularly 3 minutes to 5 minutes, more particularly 5 minutes.
In certain embodiments, the wood material is immersed in the second treatment step into the second solution for at least 5 minutes, in particular 5 minutes to 240 minutes, more particular 30 minutes to 150 minutes, most particular 120 minutes.
In certain embodiments, the second solution has a temperature of 70° C. to 110° C., in particular 70° C. to 90° C., more particular 85° C. The heat treatment will cause the decomposition of zinc ammine complex in the solution into ZnO which will deposite on the seeded wood surface.
In certain embodiments, in the first treatment step in case of the first solution comprising zinc oxide the drying of the wood material is performed at a temperature of 80° C. to 110° C., particularly 90° C. to 110° C. more particularly 110° C. The heat treatment in this step will decompose the zinc ammine complex binding on the wood surface to form a ZnO seeding layer.
In certain embodiments, in the first treatment step in case the first solution comprising zinc oxide the drying of the wood material is performed for at least 2 minutes, particularly 2 to 30 minutes, more particularly 10 minutes.
In certain embodiments, in the second treatment step drying of the wood material, particularly for removing the solvent, is performed at a temperature of 50° C. to 80° C., in particular 60° C. to 80° C., more particular 65° C. for at least 2 hours, in particular 2 h to 16 h, more particular 4 h to 12 h.
In certain embodiments, the zinc compound of the second solution is selected from zinc oxide, zinc nitrate and zinc acetate.
In certain embodiments, the second solution comprises zinc oxide or zinc nitrate with a concentration higher than that of a saturated zinc oxide or zinc nitrate solution, in particular a zinc oxide solution with a concentration higher than that of a saturated zinc oxide solution.
In the context of the present specification the term saturated solution refers to a solution of a substance that cannot dissolve more of that substance under standard conditions. Addition of more substance yields a separate phases (solid). The concentration of a saturated solution depends on parameters such as temperature, pressure, solvent, pH and other compounds present in the solution. Changes to these parameters that further increase the solubility of the substance results in solutions that with a concentration that is higher than that of a saturated solution.
In certain embodiments, the second solution comprises zinc oxide with a concentration of 40 to 65 mM, particularly 40 to 55 mM, more particularly 50 mM.
In certain embodiments, the second solution comprises zinc nitrate with a concentration of 40 to 65 mM, particularly 40 to 55 mM more particularly 50 mM.
In certain embodiments, the second solution comprises zinc acetate with a concentration of 40 to 110 mM, particularly 50 to 100 mM.
In certain embodiments, the second solution comprises zinc oxide and ammonium hydroxyl.
In certain embodiments, the second solution comprises zinc oxide and at least one ammonium salt.
In certain embodiments, the second solution comprises zinc oxide and ammonium hydroxyl and at least one ammonium salt.
In certain embodiments, the second solution comprises zinc nitrate and hexamethylentetramine (HMTA; CAS 100-97-0).
In certain embodiments, the second solution comprises zinc nitrate, hexamethylentetramine and at least one ammonium salt.
In certain embodiments, the second solution comprises zinc acetate and hexamethylentetramine.
In certain embodiments, the second solution comprises zinc acetate, hexamethylentetramine and at least one ammonium salt.
Ammonium salt or HMTA, particular ammonium salt, is used to increase the solubility of zinc compounds, in particular zinc oxide, zinc nitrate or zinc acetate, without increasing the pH value of the second solution.
In certain embodiments, the at least one ammonium salt is selected from ammonium citrate [(NH4)3(C6H5O7)], ammonium nitrate [NH4NO3], ammonium acetate [CH3COONH4] and ammonium chloride [NH4Cl].
In certain embodiments, the at least one ammonium salt is selected from ammonium citrate [(NH4)3(C6H5O7)]. In certain embodiments, the at least one ammonium salt is selected from ammonium citrate [(NH4)3(C6H5O7)] and a further ammonium salt is selected from the group of ammonium nitrate [NH4NO3], ammonium acetate [CH3COONH4] and ammonium chloride [NH4Cl], particularly the further ammonium salt is ammonium nitrate [NH4NO3].
In certain embodiments, the second solution comprises zinc acetate, hexamethylentetramine and at least ammonium citrate.
In certain embodiments, the ammonium citrate concentration is between 3 mM and 6 mM.
In certain embodiments, the second solution comprises aluminiumnitrate.
In certain embodiments, the second solution is an aqueous solution.
In certain embodiments, the wood material in the second treatment step is immersed into the second solution for at least 5 minutes, particularly 5 minutes to 240 minutes, more particularly 30 minutes to 150 minutes, most particularly 120 minutes.
In certain embodiments the second solution in the second treatment step has a temperature of 70° C. to 110° C., particularly 70° C. to 90° C., more particularly 85° C.
In certain embodiments, the wood material in the second treatment step is dried at a temperature of 50° C. to 80° C., particularly 60° C. to 80° C., more particularly 65° C.
In certain embodiments, the wood material in the second treatment step is dried for at least 2 hours, particularly 2 h to 16 h, more particularly 4 h to 12 h.
In certain embodiments, the time and temperature of drying in the second treatment step may be increased depending on the size of the wood material.
A non-limiting example is wood material of the dimensions radial (R)×tangential (T)×longitudinal (L) dimensions: 5×25×40 mm requiring a drying of at least 5 minutes at 60° C., preferably 60° C. for 2 hours. Wood material of smaller or larger dimension might require proportionally shorter or longer, respectively and/or lower temperatures. In general requires wood material of larger dimensions longer drying time than wood material of smaller dimensions.
In certain embodiments, the first and/or second treatment step is repeated at least once.
In certain embodiments, the method according to the first aspect of the invention in case of the first solution comprising zinc oxide further comprises a stabilization step. The stabilization step is further comprising in this sequential order the steps of:
In certain embodiments, the stabilizing solution comprises a precursor of SiO2, water and organic solvent and ammonium hydroxide.
In certain embodiments, the stabilizing solution comprises as a precursor of SiO2 tetraethyl orthosilicate.
In certain embodiments, the stabilizing solution comprises ammonium hydroxide, tetraethyl orthosilicate as a precursor of SiO2, and water and organic solvent, particularly water and alcohol, more particularly water and ethanol.
In certain embodiments, the stabilizing solution comprises water and organic solvent, particularly water and alcohol, more particularly water and ethanol.
In certain embodiments, the stabilizing solution comprises ammonium hydroxide.
In certain embodiments, the wood material is immersed into the stabilizing solution for 1 h to 6 h, particularly 2 h to 5 h and more particularly 3 h to 4 h.
In certain embodiments, in the stabilization solution the volume ratios of water to organic solvent, in particular alcohol, more particularly ethanol, ranges from 20:100 to 20:70.
In certain embodiments, in the stabilization solution the volume ratios of water to ammonium hydroxide range from 20:0.5 to 20:1.5.
In certain embodiments, in the stabilization solution the volume ratios of water to tetraethyl orthosilicate range from 20000:10 to 20000:60.
In certain embodiments, in the stabilization solution the volume ratios of:
Another sub aspect of the invention relates to a method for treatment of wood material that comprises provision of a first solution comprising titanium (IV) isopropoxide (TTIP; CAS No: 546-68-9) in an organic solvent in particular an alcohol, more particular ethanol or isopropanol, most particularly ethanol.
In certain embodiments, the method for treatment of wood material comprises the steps of
In certain embodiments, steps i. to iii. are repeated at least once.
In certain embodiments, the first solution additionally comprises Ce(NH4)2(NO3)6.
In certain embodiments, steps ii and iii are repeated up to 15 times, in particular 5 to 10 times.
In certain embodiments, the first solution additionally comprises Ce(NH4)2(NO3)6 and steps ii and iii are repeated up to 15 times, in particular 5 to 10 times.
In certain embodiments, the first solution comprising titanium(IV) isopropoxide (TTIP) with a concentration from 1 wt % to 10 wt %, in particular 2 wt % to 8 wt %, more particular 4 wt % to 6 wt %.
In certain embodiments, the first solution is additionally comprising Ce(NH4)2(NO3)6, with a molar ratio of TTIP to Ce(NH4)2(NO3)6 ranging from 220:1 to 220:30.
In certain embodiments, in the first treatment step the wood material is immersed into the first solution comprising TTIP for 12 hours up to 36 hours, in particular 14 hours to 24 hours, more particular 24 hours.
In certain embodiments, in the first treatment step the wood material is immersed into the first solution comprising additionally Ce(NH4)2(NO3)6 for 6 hours to 60 hours, in particular for 24 hours to 48 hours, more particular 48 hours.
The wood material is immersed in the first solution and afterwards transferred to an oven suitable for drying of the wood material.
In certain embodiments, in the first treatment step in case of the first solution comprising TTIP drying of the wood material is performed at a temperature between 50° C. to 200° C.
In certain embodiments, the drying time is at least 1 hour to 6 hours.
In certain embodiments, in the first treatment step in case of the first solution comprising TTIP drying of the wood material is performed in three steps:
wherein the drying time is:
In certain embodiments, in case of the first solution comprising additionally Ce(NH4)2(NO3)6 drying of said wood material is performed at 50° C. to 80° C., in particular at 65° C.
The drying step helps removing the alcohol in the as formed TiO2 xerogel.
In certain embodiments, the method for treatment of wood material according to claim 12, wherein the wood material of step ii. is pre-treated by soaking the wood material into an aqueous salt solution for least 12 h.
In certain embodiments, the method for treatment of wood material according to claim 18, wherein a drying process at room temperature for more that 24 h or an accelerated drying in an oven at 65° C. for more than 6 h is applied to the pre-treated wood material.
In certain embodiments, the aqueous salt solution comprises at least one of the salts is selected from FeCl2, FeCl3, Fe(NO3)2, Fe(NO3)3, Ce(NO3)3, CeCl3, Ce(NH4)2(NO3)6, CuCl, CuBr, Cu(NO3)2, in particular from Ce(NO3)3 and Fe(NO3)3, more particularly from Ce(NO3)3.
The above mentioned salts, particularly Ce(NO3)3 or Fe(NO3)3, provide a buffer layer between the wood surface and TiO2 layer to separate the direct contact between TiO2 and wood. Secondly, the metal ions that have multi chemical valence, such as Ce3+ and Fe3+′ may catch the radicals generate in wood under UV exposure and change their chemical valence. For instance, Ce3+ to Ce4+. Therefore, it can suppress the radicals inside wood for the purpose of UV protection.
In certain embodiments, the concentration of the salt in aqueous salt solution is ranging from 0.5 mM to 50 mM, in particular 1.5 mM to 20 mM, in more particular 10 mM.
A non-limiting example is wood material of the dimensions radial (R)×tangential (T)×longitudinal (L) dimensions: 5×25×40 mm requiring a drying of at least 5 minutes at 60° C., preferably 60° C. for 2 hours. Wood material of smaller or larger dimension might require proportionally shorter or longer, respectively and/or lower temperatures. In general requires wood material of larger dimensions longer drying time than wood material of smaller dimensions.
In certain embodiments according to the first aspect of the invention, the method further comprises a hydrophobization step comprising in this sequential order, the steps of:
In certain embodiments, the method comprises, in case of the first solution comprising ZnO, the first treatment step, the second treatment step, the stabilization step and a hydrophobization step.
In certain embodiments, the method comprises the first treatment step, the second treatment step and a hydrophobization step.
In certain embodiments, the method comprises, in case of the first solution comprising ZnO, the first treatment step, the second treatment step and the stabilization step.
In certain embodiments, the hydrophobic solution comprises an organic solvent particularly alkanes or alcohols, more particularly hexane, ethanol or methanol.
In certain embodiments, the hydrophobic solution comprises a hydrophobic molecule selected from:
In certain embodiments in the hydrophobization step the immersion time has a duration of 0.5 hours to 12 hours, particularly 2 h to 12 hours, more particularly 4 h to 12 h, most particularly 12 h.
In certain embodiments in the hydrophobization step the heat treatment is performed at a temperature of 50° C. to 80° C., particularly 60° C. to 70° C., more particularly 65° C., for a duration of 0.5 hours to 3 hours, particularly 3 hours.
According to a second aspect of the invention a wood material is provided. The wood material is characterized by the visibility of the natural appearance of the surface of the wood material and at least one of the following properties.
Wood material has a characteristic surface comprising the grain and texture of the wood material. These surface properties are the reason for the aesthetic appearance of wood surfaces and are therefore advantageous properties of wood materials.
In some embodiments the contact angle of a water drop on the surface of the wood material is measured. The term contact angle refers to the angle formed by the intersection of the liquid-solid interface and the liquid-vapor interface. In case the liquid used is water a contact angle smaller than 90° indicates a hydrophilic surface, a contact angle between 90° and 150° indicates a hydrophobic surface and contact angles above 150° indicate a superhydrophobic surface. In other words the higher the contact angle between a solid surface and a water droplet is the less hydrophilic and the more hydrophobic the solid surface is. A more adequate characterization of the wettability properties of surface can be obtained by measuring dynamic contact angles. The contact angle measured by expanding the liquid is referred to as the advancing contact angle and the contact angle formed by contracting the liquid is referred to as the receding contact angle. Known methods to measure a contact angle include direct measurement by goniometers. In the context of this specification a rolling-off angle refers to the tilting angle of a surface when a drop of water on this surface starts to roll-off the tilted surface. The smaller a rolling off angle is the less strongly the water drop adheres to the surface.
In some embodiments the colour of the wood material can be measured by commercially available devices such as for example the Chroma Meter CR-200 (MINOLTA, Japan). The colours are recorded in the CIE L*a*b* colourspace, whereas the dimensions L*a*b* can be used to calculate the total colour change (ΔE) according to this equation ΔE=√{square root over (ΔL2+Δa2+Δb2)}.
In the context of the present specification, the term CIE L*a*b* colourspace refers to an absolute colour space adopted by the International Commission on Illumintaion (CIE) and includes all perceivable colours. It is defined by the dimension L* for lightness, a* for red/green opponent colours and b* for yellow/blue opponent colours. The lightness, L*, represents black at L*=0, and white at L*=100. The red/green opponent colours are represented by a*, with green at negative a* values and red at positive a* values. The yellow/blue opponent colours are represented by b*, with blue at negative b* values and yellow at positive b* values. Total colour changes of perceivable colours can be calculated from L*, a* and b* according to the following equation (ΔE=√{square root over (ΔL2+Δa2+Δb2)}). The factors L*, a* and b* can be measured with commercially available devices such as for example the Chroma Meter CR-200 (MINOLTA, Japan).
In some embodiments UV exposure is performed with an electrical input of the lamp of 400 W. The lamp has sunlight simulation spectra.
Resistance of wood material to weathering can be measured in wood material subject to accelerated weathering in suitable devices. One such example of a suitable device is the QUV Accelerated Weathering Tester (Q-LAB, United States) that follows the European standard EN 927-6:2006 (E). In some embodiments an exposure cycle of one week consists of a condensation period followed by a sub-cycle of water spray and UV-A 340 nm irradiation as given in Table 1.
Resistance of wood material to mechanical damage can be tested with devices such as a micro scratch tester. These devices allow to physically damage the surface and uppermost layers of the wood material in a defined way. The applied force as well as the depth of penetration can be adjusted precisely. Microscopy can be used to determine the damage done to surface coatings as well as to the surface of the wood material itself.
Simpler and non-quantitative methods to assess the resistance of wood material to mechanical damage are the tape-and-peel test or the blade scratch test. Whereas the former test comprises the use of an adhesive tape that is repeatedly attached and removed to the surface, the latter comprises the use of a blade that is scratched repeatedly on the surface of the wood material. Microscopy techniques can in both cases be used to assess if the damage is only restricted to the directly damaged area or if parts of the surface coating or wood surface is peeling off.
A coating of which at least a single layer, that can impart the properties of the coating to the wood material, remains intact after mechanical insult, such as a tape-and-peel test or a blade scratch test, is deemed resistant to mechanical damage.
According to a third aspect of the invention a wood material particularly comprising the features according to the second aspect of the invention obtainable by a process according to the method of the first aspect of the invention is provided.
In certain embodiments according to the second and third aspect of the invention the wood material is a surface coating for wood material.
In the context of the present specification, the term wood material refers to any material comprising wood as an essential part, in particular solid wood products, wood-containing base materials, wood-based materials, semi-finished products or components.
In the context of the present specification, the term wood refers to a material comprising the three primary components lignin, cellulose, and hemicellulose. Lignin is a three dimensional aromatic polymer that is part of the cell wall matrix. Cellulose is a non-branching chain of up to several thousand glucose molecules. In contrast hemicelluloses are branched polysaccharides comprising different sugar molecules such as glucose, xylose, mannose, galactose etc. Wood typically comprises about 40 to 50 wt. % of cellulose, about 20 to 35 wt. % of hemicellulose, and about 15 to 30 wt. % of lignin.
In the context of the present specification, the term solid wood product refers to timber products, which consist basically of solid wood or solid wood parts. Solid wood describes wood-containing base materials, whose profiles are carved out from a tree trunk and are potentially processed further by cutting/machining, without changing the texture of the wood. Solid wood products can be used to produce components, semi-finished products or products.
In the context of the present specification, the term wood-containing base materials refers to all wood-containing materials, which can be used as base materials for the production of wood-based material, components, semi-finished products, products or solid wood products. Wood-containing base materials can include wooden particles or wood pieces, for instance, which are used in the production of chipboards, oriented strand boards or other wood-based materials. Wood-containing base materials are especially used in the production of wood-based materials.
In the context of the present specification, the term wood-based materials refers to a material, which is re-assembled and consists of fibres, particles, or layers of wood of different shape, size and thicknesses. The particles can, for example, comprise wood strips, wood chips or wood fibers of the same or of different types of wood, of a certain size or of different sizes.
In the context of the present specification, the term semi-finished products refers to base material products, for instance a plate, a pole or a tube, which can be processed further to the actual finished product (the final product). A semi-finished product can include an appropriately cut piece of solid-wood or comprise different wood-containing base materials. According to the invention, a semi-finished product can also be wood chips or wood stripes.
In the context of the present specification, the term component refers to a part (for instance a solid wood product, a wood-containing base material and/or a wood-based material) of a larger complex. A complex can be a building or a storage product, like a showcase, or a part of furniture. The components (in particular different components) can form the complex together, given an appropriate composition.
Wherever alternatives for single separable features such as, for example, a treatment duration or temperature, a solution component or immersion duration are laid out herein as “embodiments”, it is to be understood that such alternatives may be combined freely to form discrete embodiments of the invention disclosed herein.
The invention is further illustrated by the following examples and figures, from which further embodiments and advantages can be drawn. These examples are meant to illustrate the invention but not to limit its scope.
The technical problem in wood surface modification is how to cover the rough wood surface (uneven topography with lumen and cut-open cells wall) with a continuous and complete coating of ZnO. A strong adhesion between the inorganic coating and wood surface is necessary to prevent the separation of the coating. Finally, the inorganic coating should possess a high degree of crystallinity to achieve a certain transparency for aesthetic reasons and to avoid etching under water spraying.
In this specification, a novel seeding method is disclosed to modify the wood surface with a thin seeding layer by dipping wood material into a basic solution of Zinc Oxide before drying. This liquid based seeding method enables to seed the rough wood surface completely and to form a strong interface between the seeding layer and the wood surface. By adjusting the amount of ammonium citrate in the growth process, the synthesis of ZnO nanorod arrays or dense coatings can specifically be selected. The chemical bath deposition process is illustrated in
The process of wood treatment with ZnO in basic solvent according to the invention comprises the following steps:
I. ZnO Coating
Another typical procedure for a chemical bath deposition is described below:
NH4NO3 (8.004 g, p.a. grade, Sigma-Aldrich, Belgium), ZnO powder (8.139 g, p.a. grade, Sigma Aldrich, the Netherlands) and 132 ml of NH4OH (28% in water, Alfa Aesar, Karlsruhe, Germany) were loaded into a plastic bottle before pouring deionized water until the total volume reached 2 I. The precursor solution was stirred for 12 h and stored at r.t. until usage. For the formation of dense ZnO coating, 200 ml of precursor solution was filtered (1 μm glass fibre filters) into a glass flask followed by adding 0.170 g of ammonium citrate (p.a. grade, Alfa Aesar, Karlsruhe, Germany). The pH value of the precursor solution was about 11.4. After pre-heating at 90° C. for 15 min, the seeded spruce slices were immersed into the growth solution. Chemical bath deposition was carried out at 90° C. for 150 min. After the chemical bath deposition, the wood samples were removed from the solution, washed with water, and dried in an oven at a temperature of 65° C. for 12 h. For the formation of ZnO nanorod coating, 200 ml precursor solution was filtered into a glass flask followed by adding aluminium nitrate nonahydrate (0.008 g, Sigma Aldrich, Germany) to form a precursor solution with an aluminium ions concentration of 0.1 mM. Then, the seeded spruce slice was immersed into the growth solution. Deposition was carried out at 90° C. for 30 min. After the chemical deposition, the wood samples were washed with water and dried in an oven at a temperature of 65° C. for 1 h.
II. UV and Weathering Stability Assessment
A UV curing chamber (UVACUBE 400, Honle Goup) was used as a light source for the short-time irradiation to assess the UV protection efficiency of the coating.
Exposure of the wood coating to artificial weathering using fluorescent UV lamps and water was carried out in the QUV Accelerated Weathering Tester (Q-LAB, United State) following the European standard EN 927-6:2006 (E). An exposure cycle of one week consists of a condensation period followed by a sub-cycle of water spray and UV-A 340 irradiation as given in Table 1.
Colour evaluation of the wood samples before and after UV exposure and water spraying were determined in the CIE L*, a* and b* system with the Chroma Meter CR-200 (MINOLTA, Japan). L* represents the lightness from black (0) to white (100), while a* and b* were the chromaticity indices where +a* was the red, −a* was the green, +b* was the yellow, −b* was the blue directions. The total colour change was defined according to equation (1):
ΔE=√{square root over (ΔL2+Δa2+Δb2)} (equation 1) Characterization of total colour changes
The ZnO coating of the wood surface was characterized by x-ray diffraction (XRD) (
The dense and continuous ZnO film coating on the wood surface was further investigated by SEM from radial section and cross section. It demonstrates that the wood surface is covered with a conformal ZnO film which also covers the lumen surface of the first cell layer (
The dense and continuous ZnO coating proved to be beneficial for the weathering resistance of the wood surface, which is discussed below. The coating obtained by ZnO platelets was characterised in more detail by TEM presented in
The platelet-like ZnO is highly crystalline and accumulates on the wood surface in a compact fashion, from which the hexagonal structure with clear crystal boundary could be observed on the top.
A micro scratch tester was used to characterize the practical adhesion failure of the ZnO coating with a 10 μm tip in 1 mm length (
The UV protection efficiency of the modified wood was assessed by alternating UV exposure and color measurement (
The change in chemical structure of wood was further analyzed by FT-IR spectroscopy (
Accelerated weathering tests were carried out based on the European standard: EN 927-6:2006. As a result, there is not only a colour change but also cracking observed from the bare spruce slice after the weathering test (
III. Concept Behind the Invention
Without wishing to be bound by theory the disclosed invention takes advantage of the coordination effect of Zn[(OH)x(NH3)y]2-x complexes to hydroxyl, carbonyl groups of lignocellulose to coat the uneven wood surface with conformal ZnO film via chemical bath deposition. The morphologies of ZnO coatings can be selectively controlled from rough nanorods to a continuous and dense film using different capping agents. The high crystallinity and continuity of the ZnO crystals in the dense film not only endows the coating with effective UV blocking properties, but also makes it more stable during weathering. The dense film renders the coating more transparent for preserving the aesthetic appeal of the wood surface. The study with advanced S/TEM indicates a wood surface interlocking with ZnO dendritic crystal whisker at the interface, which results in the strong interaction between the inorganic coating and the wood biopolymer.
The process of wood material preparation using Zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) and including a hydrophobization step according to the invention comprises the following steps:
I. ZnO Coating
II. Preparation of Hydrophobic Surface-Layer
The process of wood material preparation with ZnO including the addition of a SiO2 blocking layer and a hydrophobization step according to the invention comprises the following procedures:
III. ZnO Coating
IV. Preparation of SiO2 Blocking Layer
V. Preparation of Hydrophobic Surface-Layer
Compared with Existing Technologies, the Advantages of this Invention Include the Following Points:
According to the invention, a ZnO seeding layer is provided, which is strongly attached to the wood surface allowing for the growth of ZnO on the seeded wood surface by applying the growth solution. Thus, providing a unique complete coverage on the wood surface with a strong binding strength of the layer.
By controlling the morphology of ZnO in the second step, particularly by adding Al(NO3)3, a ZnO nanorod coating is provided comprising a good UV protection property. Moreover, the nanorod structures enable controlling the wood surface roughness. A superhydrophobic wood surface ca be provided by modifying the surface of ZnO nanorod with hydrophobic molecules. The ZnO nanorod coating is particularly good for indoor application.
By inducing ammonium citrate ions into the growth solution a dense and highly crystalline ZnO layer is provided. The citrate ions will cap onto the {0001} facet of the ZnO, thus, providing such a layer. The dense and continuous ZnO layer cannot scatter visible light, therefore, it is transparent. Furthermore, the layer is highly crystalline, which makes it very stable under rain washing in outdoor applications.
Protection of Wood Surface by TiO2
The coating process contains the hydrolysis initiated by the nucleophilic ligands in wood and polymerization reactions of the precursor, which is titanium tetraisopropoxide (TTIP) in this report. 2 mL TTIP was injected into 20 mL ethanol solution. Then, 2 pieces of spruce sample (50×50×5 mm in longitudinal×tangential×radical in dimension) were immersed into the mixed solution for 24 hours at room temperature. The samples were removed from the solution followed by drying in the oven at 65° C. for 2 hours, 120° C. for 1 hour and 180° C. for 0.5 hour.
TTIP treatment results in an amorphous TiO2 which covers wood the surface continuously, but without any boundary. It is a continuous thin film, which is generated by the hydrolysis of TTIP molecules initiated by the moisture in wood or the hydroxyl groups in wood. Moreover, because of the permeation of the TTIP and alcohol precursor solution into the wood, the resulted TiO2 layer not only covers the wood surface but also covers the lumen surface inside the wood.
UV Stability
The UV protection effect of the modified sample was assessed by UV exposure in the UV chamber combined with color measurement. As shown in
Transparent TiO2—CeO2 UV Protection Coating
Ce(NH4)2(NO3)6 was dissolved in 200 mL of isopropanol solution with a concentration of 1.5 mM. A total volume of 20 mL of Titanium isopropoxide (C12H28O4Ti) was added rapidly to this solution to produce a yellow precursor solution. The precursor solution was filled in a box (polypropylene) with a lid on the top.
A spruce wood panel was placed in the precursor solution. The box was put on the shaker and kept at room temperature for 48 h.
The precursor solution was removed from the box and stored in a conical flask. The wood panel was kept in the box. 4.5 mL precursor solution was dropped onto the wood surface followed by a drying step in the box at room temperature for 45 min. This process was repeated up to 5-10 times to increase the thickness of TiO2—CeO2 coating on the surface of wood panel. After that the wood panel was dried in the oven at 65° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| 15183867.9 | Sep 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/070866 | 9/5/2016 | WO | 00 |
