CN110975624A - Silicon dioxide closed porous membrane and preparation method thereof - Google Patents
Silicon dioxide closed porous membrane and preparation method thereof Download PDFInfo
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- CN110975624A CN110975624A CN201911401763.6A CN201911401763A CN110975624A CN 110975624 A CN110975624 A CN 110975624A CN 201911401763 A CN201911401763 A CN 201911401763A CN 110975624 A CN110975624 A CN 110975624A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
The invention relates to a silicon dioxide closed porous membrane and a preparation method thereof, wherein the preparation method comprises the following steps: 1. adding ethyl orthosilicate into ethanol and stirring; adding hydrochloric acid aqueous solution; adding boric acid and sodium nitrate powder into the mixed solution, stirring for 4-8 hours, sealing, standing and aging to obtain sol A; 2. adding 0.1-0.5% of polyethylene glycol as a pore-forming agent into the sol A, and uniformly mixing to obtain sol B; 3. coating the sol B on the surface of a substrate, and drying at 80-120 ℃ to obtain a film layer B; 4. coating the sol A on the film layer b, and keeping the temperature at 300-350 ℃ for 8-12 min to obtain a film layer a; 5. and (3) keeping the substrate at 500-700 ℃ for 1-6 h, and then cooling the substrate in a furnace to obtain the closed porous membrane. The closed porous membrane provided by the invention has good surface smoothness, strength and chemical stability, and also has good dielectric property, optical property and heat-insulating property while playing unique optical and thermal functions, and can be applied to related fields as a heat-insulating film, a low-refractive-index film and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic functional films, and particularly relates to an inorganic non-metallic film with a flat surface and spherical air holes densely distributed in the film and a preparation method thereof.
Background
The silicon dioxide film has a plurality of excellent physicochemical properties of permeability increasing, wear resistance and heat insulation through different preparation and surface treatment methods. Inorganic membranes are classified into two types, dense membranes and porous membranes, according to the membrane structure, while most of the inorganic membranes are dense membranes prepared by a physical method. SiO22The physical preparation method of the film comprises magnetron sputtering, electron beam evaporation, vacuum evaporation and the like. The existing material can not obtain a solid material with the refractive index lower than 1.38, and the film prepared by a physical method has a single structure, so that the wide application of the silicon dioxide film is limited. For porous SiO applied to antireflection film2The film layer is formed by accumulating silicon dioxide nano particles, and a large number of pores exist in the film layer, so that the refractive index is low; meanwhile, due to the porous structure, the porous membrane is easy to adsorb pollutants in the environment, so that the transmittance is reduced, and the environmental stability is poor. The weak mechanical strength of the nanoporous membrane materials has affected their widespread use.
Disclosure of Invention
The invention aims to solve the defects that a porous membrane existing in a silicon dioxide film in the prior art is easy to adsorb pollutants in the environment, so that the transmittance is reduced, the environmental stability is poor and the mechanical strength of the material is poor, and provides a closed porous membrane and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the silica closed porous film features its upper and lower structure, the upper layer being compact non-porous layer and the lower layer being porous layer.
The raw materials comprise tetraethoxysilane, boric acid, sodium nitrate, absolute ethyl alcohol, pure water, hydrochloric acid and the like, and the film prepared from the raw materials comprises the following components in percentage by mole: 65% -85% SiO2，5%～18%B2O3，2.5%～8%Na2O, while satisfying the molar ratio n (B)2O3):n(SiO2)＜0.28，n(Na2O):n(B2O3)＜0.26，n(H2O):n(SiO2)=6～10，n(C2H5OH):n(SiO2)=6～10。
Wherein n represents the amount of substance, unit mole, symbol mol. For example: "n (B)2O3):n(SiO2) < 0.28 "means B2O3Amount of substance and SiO2The ratio of the amounts of substances is less than 0.28, B2O3Amount of substance and SiO2The ratio of the amounts of the substances is equal to B in the porous film2O3Mole fraction and SiO2The molar fraction ratio is only a proportional relation of the contents of the components, and absolute content values are not related.
Calculating the using amount of the raw materials according to the content and the relation of the components, firstly adding ethyl orthosilicate into ethanol, fully stirring, then dropwise adding a certain volume of pure water into the mixture to dilute the mixture into hydrochloric acid aqueous solution with the pH = 1-2, then weighing boric acid and sodium nitrate powder, adding the mixed solution, and continuously stirring to completely dissolve the mixed solution until the mixed solution is clear and transparent again. Continuously stirring for 4-8 hours, sealing, standing and aging to obtain sol A.
The raw material calculation is a conventional calculation, and specific mole fractions are determined within the mole percentage content ranges of the SiO2, B2O3 and Na2O, and the specific content relation is required to satisfy n (B)2O3):n(SiO2)＜0.28，n(Na2O):n(B2O3) < 0.26. Calculating the amount of the ethyl orthosilicate substance for providing the silicon source by taking a certain amount of SiO2 as a reference, and converting to obtain a corresponding volume; respectively calculating the amounts of B2O3 and Na2O substances according to the proportional relation by taking the amount of the SiO2 substance as a reference, respectively calculating the amounts of boric acid and sodium nitrate substances serving as a boron source and a sodium source according to the calculated amounts, and converting the mass and the measured amount; according to n (H)2O):n(SiO2)=6～10，(C2H5OH):n(SiO2) Determining H according to the range of = 6-10 and the determined using amount of SiO22O and C2H5And (4) converting the amount of the OH substance into a corresponding volume, and measuring.
And taking a part of the sol A, adding polyethylene glycol which accounts for 0.1-0.5% of the sol A by mass as a pore-forming agent, stirring, and standing to obtain sol B.
Coating the sol B on the surface of a clean substrate, drying the surface in the air and drying the surface in a constant-temperature drying oven at 100 ℃ to obtain a gel film, and repeating the steps for a plurality of times to obtain a film layer B with a certain thickness. And coating the sol A on the film layer b, drying the surface of the film layer b in the air, putting the film layer b into a box-type resistance furnace at the temperature of 300-350 ℃, preserving the heat for 8-12 min, and repeating the process to obtain a film layer a with a certain thickness.
And (3) putting the film prepared by the method into a box-type resistance furnace, raising the temperature to 500-700 ℃ at a heating rate of 0.5-2 ℃/min, preserving the heat for 1-6 h, and then cooling the furnace to obtain the silicon dioxide closed porous film.
The pore-forming agent used in the silicon dioxide closed porous membrane is solid polyethylene glycol, the molecular weight is not less than 10000, and the pore-forming agent can be a combination of two or more than two pore-forming agents with different molecular weights. The closed porous film is also characterized in that spherical pores are positioned in the inner layer of the film, and the surface is dense and nonporous; the film thickness is 100-1600 nm, and the aperture size is 2-150 nm; the thickness of the upper non-porous film layer and the lower porous structure film layer can be adjusted by changing the number of the coating layers of the porous layer and the compact layer, and the aperture size can also be adjusted by the heat treatment process and the molecular weight and the proportion of the pore-forming agent.
The invention adopts the sol-gel method to prepare the closed porous SiO2The film has compact surface, uniform pores distributed inside, good strength, chemical stability, dielectric property, optical property and heat-insulating property.
Drawings
FIG. 1 is a closed porous membrane having a porous layer with a thickness greater than that of a dense layer.
FIG. 2 is a closed porous membrane having a porous layer thickness approximately equal to the dense layer.
FIG. 3 is a closed porous membrane having a porous layer with a thickness less than the dense layer.
Detailed Description
The practice of the present invention is further illustrated below with reference to specific examples, but the practice and scope of the present invention is not limited thereto.
The first embodiment is as follows:
adding 10mL of ethyl orthosilicate into 20.9mL of ethanol, fully stirring, then dropwise adding 6.5mL of 0.1mol/L hydrochloric acid aqueous solution, weighing 1.11g of boric acid and 0.38g of sodium nitrate powder, adding the mixed solution, and continuously stirring until the mixed solution is completely dissolved until the mixed solution is clear and transparent again. Stirring for 4 hours, sealing, standing and aging to obtain sol A.
And taking a part of the sol A, adding polyethylene glycol 20000 which accounts for 0.3 mass percent of the sol A and is used as a pore-forming agent, stirring, and standing to obtain sol B.
And (3) coating a film by a dip-coating method, namely dipping a clean silicate glass substrate into the sol B at a dipping speed and a pulling speed of 130mm/min for 30 s. And (3) after the surface is slowly dried in the atmosphere, putting the dried surface into a constant-temperature drying oven to be dried at 100 ℃ to obtain a film layer b with a certain thickness.
Coating a layer of sol A on the substrate coated with the film layer b, drying in the atmosphere, and then putting the substrate into a 350 ℃ box-type resistance furnace for heat preservation for 10min to obtain a film layer a with a certain thickness.
And (3) putting the film prepared by the method into a box-type resistance furnace, heating to 550 ℃ at the heating rate of 2.5 ℃/min, preserving the heat for 2 hours, and then cooling the furnace to obtain the silicon dioxide closed porous film. The closed porous membrane has a porous layer with a single thickness and a non-porous layer with a single thickness, as shown in a scanning electron microscope picture of a film section shown in FIG. 1.
The second embodiment is as follows:
adding 10mL of ethyl orthosilicate into 20.9mL of ethanol, fully stirring, then dropwise adding 6.5mL of 0.1mol/L hydrochloric acid aqueous solution, weighing 1.11g of boric acid and 0.38g of sodium nitrate powder, adding the mixed solution, and continuously stirring until the mixed solution is completely dissolved until the mixed solution is clear and transparent again. Stirring for 4 hours, sealing, standing and aging to obtain sol A.
And taking a part of the sol A, adding 0.3 mass percent of polyethylene glycol 20000 serving as a pore-forming agent into the sol A, stirring, and standing to obtain sol B.
And (3) coating a film by a dip-coating method, namely dipping a clean silicate glass substrate into the sol B at a dipping speed and a pulling speed of 130mm/min for 30 s. Drying in the atmosphere, and drying in a constant temperature drying oven at 100 deg.C, repeating the process once to obtain a film layer b with a certain thickness.
Coating the sol A on the film layer b, drying in the atmosphere, and then putting into a 300 ℃ box-type resistance furnace for heat preservation for 8 min; and repeating coating and heat preservation once to obtain a film layer a with a certain thickness.
And (3) putting the film prepared by the method into a box-type resistance furnace, heating to 550 ℃ at the heating rate of 2.5 ℃/min, preserving the heat for 3 hours, and then cooling in the furnace to obtain the closed porous film. The closed porous membrane has two-layer thick porous layer and two-layer thick non-porous layer, as shown in figure 2 of the thin film section of the scanning electron microscope picture.
Example three:
adding 10mL of ethyl orthosilicate into 18mL of ethanol, fully stirring, then dropwise adding 6.5mL of 0.1mol/L hydrochloric acid aqueous solution, weighing 0.56g of boric acid and 0.19g of sodium nitrate powder, adding the mixed solution, and continuously stirring until the mixed solution is completely dissolved until the mixed solution is clear and transparent again. Stirring for 4 hours, sealing, standing and aging to obtain sol A.
And taking a part of the sol A, adding polyethylene glycol 20000 accounting for 0.15 percent of the mass of the sol and polyethylene glycol 40000 accounting for 0.15 percent of the mass of the sol as pore-forming agents, stirring, and standing to obtain sol B.
And (3) coating a film by a dip-coating method, namely dipping a clean quartz glass substrate into the sol B at a dipping speed and a pulling speed of 130mm/min for 30 s. Drying in the atmosphere, and drying in a constant temperature drying oven at 100 deg.C to obtain a film layer b with a certain thickness.
Coating the sol A on the film layer b, drying in the atmosphere, and then putting into a 300 ℃ box-type resistance furnace for heat preservation for 8 min; and repeating the coating and heat preservation for two times to obtain a film layer a with a certain thickness.
And (3) putting the film prepared by the method into a box-type resistance furnace, heating to 680 ℃ at the heating rate of 0.5 ℃/min, preserving the heat for 2 hours, and then cooling the furnace to obtain the closed porous film. The closed porous membrane has a porous layer with single-layer thickness and a compact non-porous layer with three-layer thickness, and the difference of the pore size is larger than that of a porous membrane prepared by only adding the same polyethylene glycol, such as a scanning electron microscope picture of a thin membrane section shown in figure 3.
Example four:
adding 10mL of ethyl orthosilicate into 20.9mL of ethanol, fully stirring, then dropwise adding 6.5mL of 0.05mol/L hydrochloric acid aqueous solution, weighing 1.11g of boric acid and 0.38g of sodium nitrate powder, adding the mixed solution, and continuously stirring until the mixed solution is completely dissolved until the mixed solution is clear and transparent again. Stirring for 4 hours, sealing, standing and aging to obtain sol A.
And taking a part of the sol A, adding polyethylene glycol 100000 which accounts for 0.4 percent of the mass of the sol and is used as a pore-forming agent, stirring, and standing to obtain sol B.
Cleaning an aluminosilicate glass substrate, then placing the aluminosilicate glass substrate on a rotary spin coater for coating, and dropwise coating the sol B on the center of the substrate, wherein the rotation speed is 3000r/min, and the spin coating time is 15 s. Drying in the atmosphere, drying in a constant temperature drying oven at 100 deg.C, and repeating the coating process for three times to obtain a film layer b with a certain thickness.
And coating a layer of sol A on the film layer b, drying in the atmosphere, and then putting into a 350 ℃ box-type resistance furnace for heat preservation for 10min to obtain a film layer a with a certain thickness.
And (3) putting the film prepared by the method into a box-type resistance furnace, heating to 600 ℃ at the heating rate of 0.5 ℃/min, preserving the heat for 2 hours, and then cooling in the furnace to obtain the closed porous film. The closed porous membrane has a porous layer of four thicknesses and a non-porous dense layer of a single thickness.
Claims (3)
1. A silicon dioxide closed porous membrane and a preparation method thereof, wherein the porous membrane comprises the following substances in molar fraction ratio: 65% -85% SiO2，5%～18%B2O3，2.5%～8%Na2O, while satisfying the molar ratio n (B)2O3):n(SiO2)＜0.28，n(Na2O):n(B2O3)＜0.26，n(H2O):n(SiO2)=6～10，n(C2H5OH):n(SiO2) = 6-10, characterized by comprising the following steps:
(1) calculating the usage amount of each raw material according to the content proportion relation of the molar fraction ratio of each substance component of the porous membrane, firstly adding tetraethoxysilane into ethanol, and fully stirring; then dropwise adding a certain volume of pure water into the mixture to dilute the mixture into hydrochloric acid aqueous solution with the pH = 1-2; weighing boric acid and sodium nitrate powder, adding the mixed solution, continuously stirring to completely dissolve the boric acid and sodium nitrate powder until the mixed solution is clear and transparent again, continuously stirring for 4-8 hours, sealing, standing and aging to obtain sol A;
(2) taking a part of the sol A, adding polyethylene glycol which is 0.1-0.5% of the amount of the taken sol A and is used as a pore-forming agent, fully stirring the sol A and the polyethylene glycol until the sol A and the polyethylene glycol are uniformly mixed, and standing to obtain sol B;
(3) coating the sol B on the surface of a clean substrate, and drying the surface in the air and drying the surface in a constant-temperature drying oven at the temperature of 80-120 ℃ to obtain a gel film; repeating the step for 1-5 times to obtain a film layer b with the required thickness;
(4) coating the sol A on the film layer b, drying the surface in the air, and putting the film into a 300-350 ℃ box-type resistance furnace for heat preservation for 8-12 min; repeating the steps for 1-5 times to obtain a film layer a with the required thickness;
(5) and (3) putting the substrate with the prepared film layer a into a box-type resistance furnace, raising the temperature to 500-700 ℃ at the heating rate of 0.5-2 ℃/min, preserving the heat for 1-6 h, and then cooling the furnace to obtain the closed porous film.
2. The silica-closed porous membrane and the method for preparing the same as claimed in claim 1, wherein the pore-forming agent is solid polyethylene glycol, the molecular weight is not less than 10000, and the pore-forming agent can be a combination of two or more different molecular weights.
3. The silica-closed porous membrane and the method for preparing the same according to claims 1 and 2, wherein the spherical pores are located in the inner layer of the membrane, and the surface is dense and nonporous; the film thickness is 100-1600 nm, and the aperture size is 2-150 nm; the thickness of the upper non-porous film layer and the lower porous structure film layer can be adjusted by changing the number of the coating layers of the porous layer and the compact layer, and the aperture size can also be adjusted by the heat treatment process and the molecular weight and the proportion of the pore-forming agent.
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| CN116120834A (en) * | 2022-12-29 | 2023-05-16 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of closed porous flexible antireflection layer |
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Application publication date: 20200410 |