CN110370409B - Nano functional composite film prepared on surface of wood and preparation method thereof - Google Patents

Nano functional composite film prepared on surface of wood and preparation method thereof Download PDF

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Publication number
CN110370409B
CN110370409B CN201910255475.8A CN201910255475A CN110370409B CN 110370409 B CN110370409 B CN 110370409B CN 201910255475 A CN201910255475 A CN 201910255475A CN 110370409 B CN110370409 B CN 110370409B
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nanoparticles
wood
nano
tio
aqueous solution
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CN110370409A (en
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富艳春
周琳
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Nanjing Linyou Intelligent Equipment Co ltd
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Nanjing Forestry University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/007—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/32—Mixtures of different inorganic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/04—Combined bleaching or impregnating and drying of wood

Abstract

The invention provides a method for preparing a nano functional composite film on the surface of wood, belonging to the field of multilayer film layer by layer assembly on the surface of a wood material. In the invention, the multi-element nano particle aqueous solution comprises two or more than two nano particles, nano phase regions with different physicochemical properties can be formed due to different structurization caused by different nano materials, such as geometric effect, surface structure change, electronic effect and the like, and the nano phase regions have synergistic interaction of non-equilibrium state under the induction of chemical and external fields (optical field, electric field, magnetic field, thermal field and the like) at the level of molecules, thereby presenting supernormal interface physical properties in a macroscopic view and realizing the construction of the multi-element synergistic nano interface structure material on the basis of the matrix component of the wood material.

Description

Nano functional composite film prepared on surface of wood and preparation method thereof
Technical Field
The invention relates to the technical field of multilayer film layer by layer assembly on the surface of a wood material, in particular to a nano functional composite film prepared on the surface of wood and a preparation method thereof.
Background
In recent years, the explosive development of nanometer level surface and interface science provides a good opportunity for emerging cross-over of important subjects such as chemistry, physics, biology, material science, nanotechnology and the like. Various interfaces can be formed between different substances, and the novel material is created by means of the surface and the peculiar functional characteristics of the interfaces generated by the contact and fusion of heterogeneous materials.
In the prior art, the problem of poor interface physical property exists in the preparation of the nano composite film on the surface of wood.
Disclosure of Invention
In view of the above, the present invention is directed to a nano-functional composite film prepared on the surface of wood and a method for preparing the same. The nano functional composite membrane prepared by the method loads a plurality of nano materials on the surface of wood, has synergistic interaction and shows the enhancement of the physical properties of an unconventional interface in a macroscopic view.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing a nano functional composite film on the surface of wood, which comprises the following steps:
providing a chitosan cation electrolyte solution;
providing a sodium phytate anionic electrolyte solution;
providing a positively charged multi-element nanoparticle aqueous solution, wherein the positively charged multi-element nanoparticle aqueous solution comprises TiO2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles;
activating the surface of the wood to obtain a wood material with negative charges on the surface;
and sequentially immersing the wood material with negative charges on the surface into a chitosan cation electrolyte solution, a sodium phytate anion electrolyte solution and a multi-element nano particle aqueous solution with positive charges, and drying to obtain the nano functional composite membrane.
Preferably, the TiO is2Nanoparticles and the SiO2The particle size of the nanoparticles was 40 nm.
Preferably, the particle size of the ZnO nanoparticles is 30 +/-10 nm.
Preferably, the Al2O3The particle size of the nanoparticles was 30 nm.
Preferably, the ZrO2The particle size of the nano particles is less than or equal to 100 nm.
Preferably, the Fe3O4The particle size of the nano particles is less than or equal to 30 nm.
Preferably, the multi-element nanoparticle aqueous solution with positive charges comprises TiO2Nanoparticles and ZnO nanoparticles, the TiO2The mass ratio of the nano particles to the ZnO nano particles is 1: 1.
Preferably, the multi-element nanoparticle aqueous solution with positive charges comprises TiO2Nanoparticles, ZrO2Nanoparticles and Al2O3Nanoparticles of said TiO2Nanoparticles, ZrO2Nanoparticles andAl2O3the mass ratio of the nano particles is 1:1: 1.
Preferably, the multi-element nano particle water solution with positive charges comprises SiO2Nanoparticles and Fe3O4Nanoparticles of said SiO2Nanoparticles and Fe3O4The mass ratio of the nanoparticles was 1: 1.
The invention also provides a nano functional composite film prepared on the surface of the wood by the method of the technical scheme, wherein the nano functional composite film comprises TiO2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles.
The invention provides a method for preparing a nano functional composite film on the surface of wood, which comprises the following steps: providing a chitosan cation electrolyte solution; providing a sodium phytate anionic electrolyte solution; providing a positively charged multi-element nanoparticle aqueous solution, wherein the positively charged multi-element nanoparticle aqueous solution comprises TiO2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles; activating the surface of the wood to obtain a wood material with negative charges on the surface; and sequentially immersing the wood material with negative charges on the surface into a chitosan cation electrolyte solution, a sodium phytate anion electrolyte solution and a multi-element nano particle aqueous solution with positive charges, and drying to obtain the nano functional composite membrane. In the invention, the multi-element nano particle aqueous solution comprises two or more than two nano particles, nano phase regions with different physicochemical properties can be formed due to different structurization caused by different nano materials, such as geometric effect, surface structure change, electronic effect and the like, and the nano phase regions have synergistic interaction of non-equilibrium state under the induction of chemical and external fields (optical field, electric field, magnetic field, thermal field and the like) at the level of molecules, thereby showing the unconventional interface physical properties on the macroscopic scale and realizing the realization of the interface physical properties on the basis of the matrix components of the wood materialAnd constructing the multi-element synergetic nano interface structure material. The data of the examples show that the interface physical properties of the nano-functional composite film prepared by the invention are superior to those of the composite film prepared by single nano-particle.
Drawings
FIG. 1 shows the surface-formed chitosan/sodium phytate/nano TiO prepared in example 12-electron and surface scans of wood of ZnO composite films;
fig. 2 is a graph showing the ultraviolet resistance test of wood and untreated wood having composite films formed on the surfaces thereof according to example 1, comparative example 1 and comparative example 2.
Detailed Description
The invention provides a method for preparing a nano functional composite film on the surface of wood, which comprises the following steps:
providing a chitosan cation electrolyte solution;
providing a sodium phytate anionic electrolyte solution;
providing a positively charged multi-element nanoparticle aqueous solution, wherein the positively charged multi-element nanoparticle aqueous solution comprises TiO2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles;
activating the surface of the wood to obtain a wood material with negative charges on the surface;
and sequentially immersing the wood material with negative charges on the surface into a chitosan cation electrolyte solution, a sodium phytate anion electrolyte solution and a multi-element nano particle aqueous solution with positive charges, and drying to obtain the nano functional composite membrane.
The invention provides a chitosan cation electrolyte solution. In the present invention, the viscosity of the chitosan is preferably >400mPa · s.
According to the invention, chitosan is preferably dissolved in deionized water, the pH is adjusted to 2-6, and ultrasonic dispersion is carried out to obtain a chitosan cation electrolyte solution with the mass fraction of 0.05-1%.
In the present invention, the pH is preferably 2.5.
In the invention, the power of ultrasonic dispersion is preferably 400-1000W, and the time of ultrasonic dispersion is preferably 5-30 min, and more preferably 10-20 min.
The invention provides a sodium phytate anionic electrolyte solution.
The method preferably dissolves sodium phytate in deionized water, adjusts the pH value to be 2-6, and performs ultrasonic dispersion for 5-30 min under the power of 400-1000W to obtain the sodium phytate anionic electrolyte solution with the mass fraction of 0.05-1%.
The invention provides a multi-element nano particle aqueous solution with positive charge, which comprises TiO in the multi-element nano particle aqueous solution with positive charge2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles.
In the present invention, the TiO is2Nanoparticles and the SiO2The particle size of the nanoparticles is preferably 40 nm.
In the present invention, the ZnO nanoparticles preferably have a particle size of 30 ± 10 nm.
In the present invention, the Al2O3The particle size of the nanoparticles is preferably 30 nm.
In the present invention, the ZrO2The particle diameter of the nanoparticles is preferably 100nm or less.
In the present invention, the Fe3O4The particle diameter of the nanoparticles is preferably less than or equal to 30 nm.
In the present invention, the aqueous solution of the multi-component nanoparticle having positive charge preferably includes TiO2Nanoparticles and ZnO nanoparticles, the TiO2The mass ratio of the nanoparticles to the ZnO nanoparticles is preferably 1: 1.
In the present invention, the aqueous solution of the multi-component nanoparticle having positive charge preferably includes TiO2Nanoparticles, ZrO2Nanoparticles and Al2O3Nanoparticles of said TiO2Nanoparticles, ZrO2Nanoparticles and Al2O3The mass ratio of the nanoparticles is preferably 1:1: 1.
In the present invention, the aqueous solution of the plurality of positively charged nanoparticles preferably includes SiO2Nanoparticles and Fe3O4Nanoparticles of said SiO2Nanoparticles and Fe3O4The mass ratio of the nanoparticles is preferably 1: 1.
According to the invention, under the ultrasonic dispersion condition, the nano particles are preferably dispersed in deionized water, and the pH value is adjusted to be less than the isoelectric point by using a dilute hydrochloric acid solution with the concentration of 0.1mol/L, so that the nano particles are all positively charged, and the multi-element nano particle aqueous solution with the positive charge and the mass fraction of 0.05-1% is obtained.
The method carries out activation treatment on the surface of the wood to obtain the wood material with negative charges on the surface.
According to the invention, the wood is preferably soaked in 0.01-0.1 mol/L dilute hydrochloric acid for surface activation treatment for 1-5 min, and then is dried to obtain the wood material with negative charges on the surface.
The wood material with negative charges on the surface is sequentially immersed into a chitosan cation electrolyte solution, a sodium phytate anion electrolyte solution and a multi-element nano particle aqueous solution with positive charges and then dried to obtain the nano functional composite membrane.
Preferably, the wood material with negative charges on the surface is immersed into the chitosan cation electrolyte solution for 5-60 min, and then repeatedly washed and dried by distilled water to obtain wood A; immersing the wood A into sodium phytate anionic electrolyte solution for 5-60 min, and then repeatedly washing and drying the wood A with distilled water to obtain wood B; and (2) immersing the wood B into the multi-element nano particle aqueous solution with positive charges for 5-60 min, then repeatedly washing and drying by using distilled water to obtain wood C, and performing circulation for 1-10 periods by taking immersion of the sodium phytate anionic electrolyte solution and the multi-element nano particle aqueous solution with positive charges as a circulation period to obtain the nano functional composite membrane. In the present invention, it is preferable that the cycle period comprises the steps of repeatedly rinsing with distilled water and drying after each immersion of the sodium phytate anionic electrolyte solution and immersion of the positively charged multi-nanoparticle aqueous solution.
The drying method of the present invention is not particularly limited, and may be a method known to those skilled in the art.
The invention also provides a nano functional composite film prepared on the surface of the wood by the method of the technical scheme, wherein the nano functional composite film comprises TiO2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles.
In order to further illustrate the present invention, the nano-functional composite film prepared on the surface of wood and the preparation method thereof provided by the present invention are described in detail below with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
Preparation of Natural polyelectrolyte/TiO on Wood surface as described in this example2The method for preparing the ZnO binary nano particle composite film comprises the following steps:
firstly, preparing a chitosan cation electrolyte solution: dissolving chitosan in deionized water, adjusting the pH to 2.5, and performing ultrasonic dispersion for 30min under the power of 1000W to obtain a chitosan cation electrolyte solution with the mass fraction of 1%;
secondly, preparing a sodium phytate anionic electrolyte solution: dissolving sodium phytate in deionized water, adjusting pH to 2.5, and ultrasonically dispersing for 30min under 1000W power to obtain 1% sodium phytate anion electrolyte solution;
thirdly, preparing TiO with positive charges2-ZnO mixed nanoparticle aqueous solution: the feeding ratio (mass ratio) is 1:1 TiO2And ZnO nano-particles are dissolved in deionized water, and diluted hydrochloric acid solution with the concentration of 0.1mol/L is used for adjusting the pH value to be 2.5, ultrasonic dispersion is carried out for 30min under the power of 1000W, so that TiO is enabled to be2Positive charge is carried out on the ZnO nano-particles to obtain the TiO with the positive charge with the mass fraction of 1 percent2-an aqueous ZnO nanoparticle solution;
fourthly, wood surface activation treatment: soaking wood in 0.1mol/L dilute hydrochloric acid for 3min to activate the surface, and drying to obtain a wood material with negative charges on the surface;
fifthly, preparing natural polyelectrolyte/TiO on the surface of wood2-ZnO binary nanoparticle composite film: soaking wood in a chitosan solution for 60min, then repeatedly washing the wood with distilled water, and drying the wood at the temperature of 60 ℃ for 2h to obtain wood A; secondly, soaking the wood A obtained in the step I into a sodium phytate solution for 60min, then repeatedly washing the wood A with distilled water, and drying the wood A for 2h at the temperature of 60 ℃ to obtain wood B; thirdly, the wood B obtained in the second step is immersed into TiO with positive charges2Soaking in ZnO nanoparticle water solution for 60min, repeatedly washing with distilled water, and drying at 60 deg.C for 2 hr to obtain wood C; by dipping into sodium phytate solution-into TiO with positive charge2The ZnO nano particle aqueous solution is a cycle period, each time of soaking comprises the steps of repeatedly washing and drying by distilled water, and the cycle is carried out for 10 cycles in the same way as the treatment steps, so that the natural polyelectrolyte/TiO formed on the surface is obtained2-ZnO binary nano particle composite film.
Formation of Chitosan/sodium phytate/Nano TiO on the surface prepared in example 12Microstructure detection and surface element analysis of the wood of the ZnO composite film are carried out, the results are shown as an electron microscope image and a surface scanning image in fig. 1, from fig. 1, it can be seen that under a high power electron microscope, the thin film on the surface of the wood is composed of a plurality of nano particles, and through the surface scanning analysis, Zn and Ti elements appear in addition to the original C, O element on the surface of the wood, which indicates that the thin film on the surface of the wood is composed of ZnO and TiO2Is composed of nano particles.
Example 2
Preparation of Natural polyelectrolyte/TiO on Wood surface as described in this example2-ZrO-Al2O3The method for the ternary nanoparticle composite film is specifically carried out according to the following steps:
firstly, preparing a chitosan cation electrolyte solution: dissolving chitosan in deionized water, adjusting the pH to 2.5, and performing ultrasonic dispersion for 30min under the power of 1000W to obtain a chitosan cation electrolyte solution with the mass fraction of 1%;
secondly, preparing a sodium phytate anionic electrolyte solution: dissolving sodium phytate in deionized water, adjusting pH to 2.5, and ultrasonically dispersing for 30min under 1000W power to obtain 1% sodium phytate anion electrolyte solution;
thirdly, preparing TiO with positive charges2-ZrO2-Al2O3Mixing the nano particle water solution: the feeding ratio (mass ratio) is 1:1:1 TiO2、ZrO2And Al2O3Dissolving nano particles in deionized water, adjusting the pH value to be 2.5 by using a dilute hydrochloric acid solution with the concentration of 0.1mol/L, and ultrasonically dispersing for 30min under the power of 1000W to ensure that the nano particles are positively charged to obtain the TiO with positive charges with the mass fraction of 1 percent2-ZrO2-Al2O3An aqueous solution of nanoparticles;
fourthly, wood surface activation treatment: soaking wood in 0.1mol/L dilute hydrochloric acid for 3min to activate the surface, and drying to obtain a wood material with negative charges on the surface;
fifthly, preparing natural polyelectrolyte/TiO on the surface of wood2-ZrO2-Al2O3Ternary nanoparticle composite films: soaking wood in a chitosan solution for 60min, then repeatedly washing the wood with distilled water, and drying the wood at the temperature of 60 ℃ for 2h to obtain wood A; secondly, soaking the wood A obtained in the step I into a sodium phytate solution for 60min, then repeatedly washing the wood A with distilled water, and drying the wood A for 2h at the temperature of 60 ℃ to obtain wood B; thirdly, the wood B obtained in the second step is immersed into TiO with positive charges2-ZrO2-Al2O3Soaking in the nanoparticle water solution for 60min, repeatedly washing with distilled water, and drying at 60 deg.C for 2 hr to obtain wood C; by dipping into sodium phytate solution-into TiO with positive charge2-ZrO2-Al2O3The ternary nano particle aqueous solution is oneThe cycle period comprises the steps of repeatedly washing and drying by distilled water after each immersion, and is the same as the treatment steps, and the cycle is carried out for 10 cycles to obtain the natural polyelectrolyte/TiO formed on the surface2-ZrO2-Al2O3Ternary nano particle composite film.
Example 3
The preparation of natural polyelectrolyte/SiO on the surface of wood described in this example2-Fe3O4The method for the binary nano particle composite membrane is specifically carried out according to the following steps:
firstly, preparing a chitosan cation electrolyte solution: dissolving chitosan in deionized water, adjusting the pH to 2.5, and performing ultrasonic dispersion for 30min under the power of 1000W to obtain a chitosan cation electrolyte solution with the mass fraction of 1%;
secondly, preparing a sodium phytate anionic electrolyte solution: dissolving sodium phytate in deionized water, adjusting pH to 2.5, and ultrasonically dispersing for 30min under 1000W power to obtain 1% sodium phytate anion electrolyte solution;
thirdly, preparing SiO with positive charges2-Fe3O4Mixing the nano particle water solution: the feeding ratio (mass ratio) is 1:1 SiO2And Fe3O4Dissolving nano particles in deionized water, adjusting the pH value to 2.5 by using a dilute hydrochloric acid solution with the concentration of 0.1mol/L, and ultrasonically dispersing for 30min under the power of 1000W to ensure that the nano particles are positively charged to obtain the SiO with the positive charge and the mass fraction of 1 percent2-Fe3O4An aqueous solution of nanoparticles;
fourthly, wood surface activation treatment: soaking wood in 0.1mol/L dilute hydrochloric acid for 3min to activate the surface, and drying to obtain a wood material with negative charges on the surface;
fifthly, preparing natural polyelectrolyte/SiO on the surface of the wood2-Fe3O4Binary nano particle composite film: soaking wood in a chitosan solution for 60min, then repeatedly washing the wood with distilled water, and drying the wood at the temperature of 60 ℃ for 2h to obtain wood A; ② the following stepSoaking the obtained wood A in a sodium phytate solution for 60min, then repeatedly washing the wood A with distilled water, and drying the wood A at 60 ℃ for 2h to obtain wood B; thirdly, the wood B obtained in the second step is immersed into SiO with positive charges2-Fe3O4Soaking in the nanoparticle water solution for 60min, repeatedly washing with distilled water, and drying at 60 deg.C for 2 hr to obtain wood C; by dipping into sodium phytate solution-into SiO with positive charge2-Fe3O4The nano particle water solution is a cycle period, each time of soaking comprises the steps of repeatedly washing and drying by distilled water, and the cycle is carried out for 10 cycles in the same way as the treatment steps, so that the natural polyelectrolyte/SiO formed on the surface is obtained2-Fe3O4Binary nano particle composite film.
Comparative example 1
Preparation of Natural polyelectrolyte/TiO on Wood surface as described in this example2The method for preparing the nano particle composite film is specifically carried out according to the following steps:
firstly, preparing a chitosan cation electrolyte solution: dissolving chitosan in deionized water, adjusting the pH to 2.5, and performing ultrasonic dispersion for 30min under the power of 1000W to obtain a polycation electrolyte solution with the mass fraction of 1%;
secondly, preparing a sodium phytate anionic electrolyte solution: dissolving sodium phytate in deionized water, adjusting the pH to 2.5, and performing ultrasonic dispersion for 30min under the power of 1000W to obtain a polyanion electrolyte solution with the mass fraction of 1%;
thirdly, preparing TiO with positive charges2Nanoparticle aqueous solution: adding TiO into the mixture2Dissolving the nano particles in deionized water, adjusting the pH value to 2.5 by using a dilute hydrochloric acid solution with the concentration of 0.1mol/L, and ultrasonically dispersing for 30min under the power of 1000W to ensure that the TiO2The nano-particles are positively charged to obtain the TiO with positive charge with the mass fraction of 1 percent2An aqueous solution of nanoparticles;
fourthly, wood surface activation treatment: soaking wood in 0.1mol/L dilute hydrochloric acid for 3min to activate the surface, and drying to obtain a wood material with negative charges on the surface;
fifthly, preparing natural polyelectrolyte/TiO on the surface of wood2Nano particle composite film: soaking wood in a chitosan solution for 60min, then repeatedly washing the wood with distilled water, and drying the wood at the temperature of 60 ℃ for 2h to obtain wood A; secondly, immersing the wood A obtained in the fifth step into a sodium phytate solution for 60min, then repeatedly washing the wood A with distilled water and drying the wood A at the temperature of 60 ℃ for 2h to obtain wood B; thirdly, the wood B obtained in the fifth step is immersed into the TiO with positive charges2Soaking in nanoparticle water solution for 60min, repeatedly washing with distilled water, and drying at 60 deg.C for 2 hr to obtain wood C, and soaking in sodium phytate solution2The nano particle water solution is a cycle period, each time of soaking comprises the steps of repeatedly washing and drying by distilled water, and the cycle is carried out for 10 cycles in the same way as the treatment steps, so that the natural polyelectrolyte/TiO formed on the surface is obtained2The nano particle composite film is wood.
Comparative example 2
The method for preparing the natural polyelectrolyte/ZnO nanoparticle composite film on the surface of the wood is specifically carried out according to the following steps:
firstly, preparing a chitosan cation electrolyte solution: dissolving chitosan in deionized water, adjusting the pH to 2.5, and performing ultrasonic dispersion for 30min under the power of 1000W to obtain a polycation electrolyte solution with the mass fraction of 1%;
secondly, preparing a sodium phytate anionic electrolyte solution: dissolving sodium phytate in deionized water, adjusting the pH to 2.5, and performing ultrasonic dispersion for 30min under the power of 1000W to obtain a polyanion electrolyte solution with the mass fraction of 1%;
thirdly, preparing a ZnO nanoparticle aqueous solution with positive charges: dissolving ZnO nanoparticles in deionized water, adjusting pH to 2.5 with 0.1mol/L diluted hydrochloric acid solution, and ultrasonically dispersing at 1000W for 30min to obtain TiO2Positively charging the nano particles to obtain a ZnO nano particle aqueous solution with positive charges, wherein the mass fraction of the ZnO nano particle aqueous solution is 1%;
fourthly, wood surface activation treatment: soaking wood in 0.1mol/L dilute hydrochloric acid for 3min to activate the surface, and drying to obtain a wood material with negative charges on the surface;
fifthly, preparing a natural polyelectrolyte/ZnO nanoparticle composite film on the surface of the wood: soaking wood in a chitosan solution for 60min, then repeatedly washing the wood with distilled water, and drying the wood at the temperature of 60 ℃ for 2h to obtain wood A; secondly, immersing the wood A obtained in the fifth step into a sodium phytate solution for 60min, then repeatedly washing the wood A with distilled water and drying the wood A at the temperature of 60 ℃ for 2h to obtain wood B; thirdly, immersing the wood B obtained in the fifth step into ZnO nano particle water solution with positive charges for 60min, then repeatedly washing the wood B with distilled water and drying the wood B at the temperature of 60 ℃ for 2h to obtain wood C; and (3) taking the immersion of the sodium phytate solution into the ZnO nano particle aqueous solution with positive charges as a cycle period, repeatedly washing and drying the immersed sodium phytate solution with distilled water after each immersion, and circularly performing 10 cycles as in the treatment steps to obtain the wood with the natural polyelectrolyte/ZnO nano particle composite film formed on the surface.
Formation of Chitosan/sodium phytate/Nano TiO on the surface prepared in example 12Wood of-ZnO composite film, surface-formed chitosan/sodium phytate/nano TiO prepared in comparative example 12The ultraviolet resistance performance of the wood of the composite film, the wood with the chitosan/sodium phytate/nano ZnO composite film formed on the surface prepared in the comparative example 2 and the untreated wood is detected, and the result shows that as shown in fig. 2, after 720 hours of continuous ultraviolet irradiation, the lightness L of the untreated wood is obviously reduced, the red-green index a and the yellow-blue index b are obviously increased, which shows that the surface brightness of the wood is reduced, the red color and the yellow color are deepened, and the change trend is very obvious after the ultraviolet irradiation. The change trend of lightness L of the modified sample is opposite to that of the material and slightly increases, while the change trends of red green index a and yellow blue index b are the same as that of the color of the material, but the change degrees of all the color parameters are obviously smaller than that of the material sample, wherein ZnO and TiO2The ultraviolet resistance of the binary synergetic load wood is superior to that of the wood processed by single nanocrystal.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (2)

1. A method for preparing a nano functional composite film on the surface of wood is characterized by comprising the following steps:
providing a chitosan cation electrolyte solution;
providing a sodium phytate anionic electrolyte solution;
providing a positively charged multi-element nanoparticle aqueous solution, wherein the positively charged multi-element nanoparticle aqueous solution comprises TiO2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles;
activating the surface of the wood to obtain a wood material with negative charges on the surface;
sequentially immersing the wood material with negative charges on the surface into a chitosan cation electrolyte solution, a sodium phytate anion electrolyte solution and a multi-element nano particle aqueous solution with positive charges, and drying to obtain a nano functional composite membrane;
the TiO is2Nanoparticles and the SiO2The particle size of the nano particles is 40 nm;
the particle size of the ZnO nano particles is 30 +/-10 nm;
the Al is2O3The particle size of the nano particles is 30 nm;
the ZrO2The particle size of the nano particles is less than or equal to 100 nm;
said Fe3O4The particle size of the nano particles is less than or equal to 30 nm;
the multi-element nano particle aqueous solution with positive charge comprises TiO2Nanoparticles and ZnO nanoparticles, the TiO2The mass ratio of the nano particles to the ZnO nano particles is 1: 1;
the multi-element nano particle aqueous solution with positive charge comprises TiO2Nanoparticles, ZrO2Nanoparticles and Al2O3Nanoparticles of said TiO2Nanoparticles, ZrO2Nanoparticles and Al2O3The mass ratio of the nano particles is 1:1: 1;
the multi-element nano particle aqueous solution with positive charges comprises SiO2Nanoparticles and Fe3O4Nanoparticles of said SiO2Nanoparticles and Fe3O4The mass ratio of the nanoparticles was 1: 1.
2. The method of claim 1, wherein the nano-functional composite film is prepared on the surface of wood, and the nano-functional composite film comprises TiO2Nanoparticles, ZnO nanoparticles, and SiO2Nanoparticles, Al2O3Nanoparticles, ZrO2Nanoparticles and Fe3O4Two or more of the nanoparticles.
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