Aluminum phosphate hierarchical structure and preparation method thereof

Abstract

The application discloses an aluminum phosphate hierarchical structure and a preparation method thereof, and relates to the technical field of aluminum phosphate materials, and comprises the following steps: S1, a glass substrate is cleaned to remove surface impurities; S2, aluminum lactate and phosphoric acid are used as raw materials, deionized water is used as a solvent, and citric acid, oxalic acid, ethylene glycol and polyethylene glycol are added as complexing agents to prepare an aluminum phosphate plating solution; S3, the plating solution is placed on the glass substrate by using a spin coating method; S4, self-assembly drying is performed; and S5, high-temperature heat treatment is performed. The application provides an aluminum phosphate hierarchical structure, and enriches the aluminum phosphate microstructure and a control method thereof. The method is used for preparing the aluminum phosphate material with the hierarchical structure through coordination chemistry and a special plating process, and the morphology of the micro-nano structure can be controlled through a formula and a process.

Description

Technical Field

[0001] This invention relates to the field of aluminum phosphate materials technology, specifically to an aluminum phosphate hierarchical structure and its preparation method. The prepared aluminum phosphate hierarchical structure can be used for glass surface modification and belongs to an aluminum phosphate material with a special microstructure for glass surface functionalization or modification. Background Technology

[0002] Glass has a wide range of applications in daily life, including architectural glass, automotive glass, photovoltaic glass, and other application glass. Due to the different functional requirements of glass in different fields, it often undergoes relevant modification treatments. Coating the glass surface with modifying materials is a common method. Materials with special micro / nano structures often exhibit superior performance in certain specific properties compared to those without a fixed shape. Therefore, the fabrication of materials with special micro / nano structures has significant application value. In recent years, researchers have discovered that aluminum phosphate materials possess excellent hydrophilicity and low refractive index antireflective properties, showing potential application value in the field of glass modification. However, research on the construction of aluminum phosphate micro / nano or hierarchical structures is relatively scarce, necessitating further research and the development of new preparation methods to enhance its application value. Summary of the Invention

[0003] The purpose of this invention is to provide a hierarchical aluminum phosphate structure and its preparation method. This method uses coordination chemistry and a special coating process to prepare aluminum phosphate materials with a hierarchical structure. The morphology of the microstructure can be controlled by the formulation and process.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A method for preparing a hierarchical aluminum phosphate structure includes the following steps:

[0006] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities;

[0007] S2. Preparation of aluminum phosphate coating solution: using aluminum lactate and phosphoric acid as raw materials, deionized water as solvent, and adding citric acid, oxalic acid, ethylene glycol and polyethylene glycol as complexing agents;

[0008] Furthermore, the amounts of aluminum lactate and phosphoric acid used meet the following conditions: the molar ratio of Al to P is 1:1; and the concentration of Al in the aluminum phosphate coating solution is 0.01–0.3 mol / L.

[0009] Furthermore, the amount of citric acid used satisfies the molar ratio of Al to citric acid being 2:1 to 5:4.

[0010] Furthermore, the amount of oxalic acid used satisfies the molar ratio of Al to oxalic acid being 2:1 to 5:1.

[0011] Furthermore, the amount of ethylene glycol used satisfies the molar ratio of Al to ethylene glycol being 2:1 to 5:1.

[0012] Furthermore, the amount of polyethylene glycol used satisfies the molar ratio of Al to -OH being 10:1 to 1:1.

[0013] Furthermore, the average molecular weight of the polyethylene glycol is 800-1500.

[0014] S3. Apply the coating solution to the glass substrate using a spin coating method; place the glass on a spin coater and hold it in place using a vacuum system to evenly apply the coating solution to the glass.

[0015] Furthermore, the spin coater operates at a speed of 100-6000 rpm for 5-10 seconds.

[0016] S4. Perform self-assembly drying at a humidity of 5%-30% and a temperature maintained at + / - of ambient temperature.

[0017] At 5℃, the drying time is 5-60 minutes to complete the self-assembly and drying process, forming a microstructure.

[0018] By controlling the temperature within + / - 5°C of the ambient temperature during the self-assembly process, the temperature difference during the drying process can be controlled as much as possible, thereby controlling the drying process. The humidity is also controlled within a low range. Under such temperature and humidity conditions, a hierarchical structure can be formed through self-assembly.

[0019] S5. Perform high-temperature heat treatment at a temperature of 200-450℃ for a duration of 30-180 minutes.

[0020] Another objective of this invention is to provide a hierarchical aluminum phosphate structure prepared by the above-described method, which has a unique hierarchical morphology and can be used for glass surface functionalization or modification.

[0021] The beneficial effects of this invention are:

[0022] The aluminum phosphate coating solution of this invention has a unique formula, using aluminum lactate and phosphoric acid as raw materials, and adding specific amounts of citric acid, oxalic acid, ethylene glycol, and polyethylene glycol as ligands. Among them, citric acid in the ligand has a coupling effect, which can bind the aluminum phosphate precursor to the glass; at the same time, citric acid provides sites to promote nucleation; the diacid and diol in the ligand have an approximately chain-like structure, which is conducive to the formation of branches in the hierarchical structure.

[0023] This invention provides a hierarchical aluminum phosphate structure, enriching the understanding of aluminum phosphate microstructures and their control methods. This method utilizes coordination chemistry and a specialized coating process to prepare aluminum phosphate materials with a hierarchical structure, where the morphology of the micro / nano structures can be controlled through formulation and processing. Attached Figure Description

[0024] The invention will now be further described with reference to the accompanying drawings.

[0025] Figure 1 This is an optical photograph of Embodiment 1 of the present invention;

[0026] Figure 2 These are optical photographs of Embodiment 2 of the present invention;

[0027] Figure 3 These are optical photographs of Embodiment 3 of the present invention;

[0028] Figure 4 These are optical photographs of Embodiment 4 of the present invention;

[0029] Figure 5 This is an optical photograph of Embodiment 5 of the present invention. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] Example 1

[0032] A method for preparing a hierarchical aluminum phosphate structure includes the following steps:

[0033] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities;

[0034] S2. Preparation of aluminum phosphate coating solution. Aluminum lactate is used as the source material for aluminum phosphate. Weigh aluminum lactate and dissolve it in deionized water, where the Al concentration is 0.3 mol / L. Add phosphoric acid dropwise while stirring, with an Al to P molar ratio of 1:1. Add citric acid, oxalic acid, ethylene glycol, and polyethylene glycol sequentially. The molar ratio of Al to citric acid added is 5:4; the molar ratio of Al to oxalic acid added is 5:1; the molar ratio of Al to ethylene glycol added is 5:1; the average molecular weight of polyethylene glycol is 800, and the molar ratio of Al to -OH is 10:1. Stir until homogeneous and allow to stand.

[0035] S3. Apply the coating solution to the glass substrate using a spin coater. Place the glass on a spin coater (model SPS (POLOS) Spin Coator SPIN150i from Germany) and hold it in place using a vacuum system; evenly distribute the coating solution onto the glass. The spin coater speed is 500 rpm, and the time is 5 seconds.

[0036] S4. The sample is self-assembled and dried at a humidity of 5% and at ambient temperature, avoiding the introduction of heat sources, for 5 minutes to form microstructures.

[0037] S5. Perform high-temperature heat treatment at a temperature of 450℃ for 30 minutes.

[0038] Example 2

[0039] A method for preparing a hierarchical aluminum phosphate structure includes the following steps:

[0040] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities;

[0041] S2. Preparation of aluminum phosphate coating solution. Aluminum lactate is used as the source material for aluminum phosphate. Weigh aluminum lactate and dissolve it in deionized water, where the Al concentration is 0.3 mol / L. Add phosphoric acid dropwise while stirring, with an Al to P molar ratio of 1:1. Add citric acid, oxalic acid, ethylene glycol, and polyethylene glycol sequentially. The molar ratio of Al to citric acid added is 5:4; the molar ratio of Al to oxalic acid added is 5:1; the molar ratio of Al to ethylene glycol added is 5:1; the average molecular weight of polyethylene glycol is 1000, and the molar ratio of Al to -OH is 10:1. Stir until homogeneous and allow to stand.

[0042] S3. Apply the coating solution to the glass substrate using a spin coater. Place the glass on a spin coater (model SPS (POLOS) Spin Coator SPIN150i from Germany) and hold it in place using a vacuum system; evenly distribute the coating solution onto the glass. The spin coater speed is 500 rpm, and the time is 5 seconds.

[0043] S4. The sample is self-assembled and dried at a humidity of 10% and at ambient temperature, avoiding the introduction of heat sources, for 10 minutes to form microstructures.

[0044] S5. Perform high-temperature heat treatment at 400℃ for 30 minutes.

[0045] Example 3

[0046] A method for preparing a hierarchical aluminum phosphate structure includes the following steps:

[0047] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities;

[0048] S2. Preparation of aluminum phosphate coating solution. Aluminum lactate is used as the source material for aluminum phosphate. Weigh aluminum lactate and dissolve it in deionized water, where the Al concentration is 0.1 mol / L. Add phosphoric acid dropwise while stirring, with an Al to P molar ratio of 1:1. Add citric acid, oxalic acid, ethylene glycol, and polyethylene glycol sequentially. The molar ratio of Al to citric acid added is 5:3; the molar ratio of Al to oxalic acid added is 3:1; the molar ratio of Al to ethylene glycol added is 3:1; the average molecular weight of polyethylene glycol is 1000, and the molar ratio of Al to -OH is 5:1. Stir until homogeneous and allow to stand.

[0049] S3. Apply the coating solution to the glass substrate using a spin coater. Place the glass on a spin coater (model SPS (POLOS) Spin Coator SPIN150i from Germany) and hold it in place using a vacuum system; evenly distribute the coating solution onto the glass. The spin coater speed is 500 rpm, and the time is 5 seconds.

[0050] S4. The sample is self-assembled and dried at a humidity of 10% and at ambient temperature, avoiding the introduction of heat sources, for 10 minutes to form microstructures.

[0051] S5. Perform high-temperature heat treatment at a temperature of 250℃ for 180 minutes.

[0052] Example 4

[0053] A method for preparing a hierarchical aluminum phosphate structure includes the following steps:

[0054] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities;

[0055] S2. Preparation of aluminum phosphate coating solution. Aluminum lactate is used as the source material for aluminum phosphate. Weigh aluminum lactate and dissolve it in deionized water, where the Al concentration is 0.1 mol / L. Add phosphoric acid dropwise while stirring, with an Al to P molar ratio of 1:1. Add citric acid, oxalic acid, ethylene glycol, and polyethylene glycol sequentially. The molar ratio of Al to citric acid added is 5:3; the molar ratio of Al to oxalic acid added is 3:1; the molar ratio of Al to ethylene glycol added is 3:1; the average molecular weight of polyethylene glycol is 1000, and the molar ratio of Al to -OH is 5:1. Stir until homogeneous and allow to stand.

[0056] S3. Apply the coating solution to the glass substrate using a spin coater. Place the glass on a spin coater (model SPS (POLOS) Spin 150i from Germany) and hold it in place using a vacuum system; evenly distribute the coating solution onto the glass. The spin coater speed is 1000 rpm, and the time is 8 seconds.

[0057] S4. The sample is self-assembled and dried at a humidity of 10% and at ambient temperature, avoiding the introduction of heat sources, for 20 minutes to form microstructures.

[0058] S5. Perform high-temperature heat treatment at a temperature of 450℃ for 30 minutes.

[0059] Example 5

[0060] A method for preparing a hierarchical aluminum phosphate structure includes the following steps:

[0061] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities;

[0062] S2. Preparation of aluminum phosphate coating solution. Aluminum lactate is used as the source material for aluminum phosphate. Weigh aluminum lactate and dissolve it in deionized water, where the Al concentration is 0.05 mol / L. Add phosphoric acid dropwise while stirring, with an Al to P molar ratio of 1:1. Add citric acid, oxalic acid, ethylene glycol, and polyethylene glycol sequentially. The amount of citric acid added is in an Al to citric acid molar ratio of 2:1; the amount of oxalic acid added is in an Al to oxalic acid molar ratio of 2:1; the amount of ethylene glycol added is in an Al to ethylene glycol molar ratio of 2:1; the average molecular weight of polyethylene glycol is 1500, and the amount added is in an Al to -OH molar ratio of 1:1. Stir until homogeneous and then let stand.

[0063] S3. Apply the coating solution to the glass substrate using a spin coater. Place the glass on a spin coater (model SPS (POLOS) Spin Coator SPIN150i from Germany) and hold it in place using a vacuum system; evenly distribute the coating solution onto the glass. The spin coater speed is 3000 rpm, and the time is 5 seconds.

[0064] S4. The sample is self-assembled and dried at a humidity of 5% and at ambient temperature, avoiding the introduction of heat sources, for 60 minutes to form microstructures.

[0065] S5. Perform high-temperature heat treatment at 400℃ for 30 minutes.

[0066] Figures 1-5 As shown, these are optical photographs of the aluminum phosphate hierarchical structures obtained in Examples 1-5, respectively.

[0067] The above detailed embodiments provide a specific description of the analytical methods involved in this invention. It should be noted that the above description is only intended to help those skilled in the art better understand the methods and ideas of this invention, and is not intended to limit the scope of the invention. Without departing from the principles of this invention, those skilled in the art can make appropriate adjustments or modifications to this invention, and such adjustments and modifications should also fall within the protection scope of this invention.

Claims

1. A method for producing an aluminum phosphate hierarchical structure, characterized by, The method comprises the following steps: S1. The glass substrate is sequentially cleaned by alkali solution and acid solution to remove surface impurities; S2. An aluminum phosphate plating solution is prepared: lactic acid aluminum and phosphoric acid are used as raw materials, deionized water is used as solvent, and citric acid, oxalic acid, ethylene glycol, and polyethylene glycol are added as complexing agents; S3. The plating solution is placed on the glass substrate by spin coating: the glass is placed on a spin coater, and the plating solution is uniformly placed on the glass by a vacuum system; S4. Self-assembly drying is performed: the humidity is 5%-30%, the temperature is kept at ambient temperature ±5℃, the time is 5-60 min, and the self-assembly drying is completed to form a microstructure; S5. High-temperature heat treatment is performed: the heat treatment temperature is 200-450℃, and the heat treatment time is 30-180 min.

2. The method for preparing an aluminum phosphate hierarchical structure according to claim 1, characterized in that, The amounts of the lactic acid aluminum and the phosphoric acid satisfy the following conditions: the molar ratio of Al element to P element is 1:1; and the concentration of Al in the aluminum phosphate plating solution is 0.01-0.3 mol / L.

3. The method for preparing an aluminum phosphate hierarchical structure according to claim 1, characterized in that, The amount of the citric acid satisfies the molar ratio of Al to citric acid is 2:1-5:

4.

4. The method for preparing an aluminum phosphate hierarchical structure according to claim 1, characterized in that, The amount of the oxalic acid satisfies the molar ratio of Al to oxalic acid is 2:1-5:

1.

5. The method for preparing a hierarchical aluminum phosphate structure according to claim 1, characterized in that, The amount of the ethylene glycol satisfies the molar ratio of Al to ethylene glycol is 2:1-5:

1.

6. The method of claim 1, wherein the aluminum phosphate hierarchical structure is prepared by the steps of: The amount of the polyethylene glycol satisfies the molar ratio of Al to hydroxyl is 10:1-1:

1.

7. The method for preparing a hierarchical aluminum phosphate structure according to claim 1, characterized in that, The average molecular weight of the polyethylene glycol is 800-1500.

8. The method for preparing a hierarchical aluminum phosphate structure according to claim 1, characterized in that, In step S3, the rotation speed of the spin coater is 100-6000 rpm, and the time is 5-10 s.

9. An aluminum phosphate hierarchical structure, characterized in that, Prepared according to any one of claims 1-8.

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