A kind of copper penny grass leaf and annular aluminum phosphate and its controllable preparation method

Abstract

The application discloses a kind of copper penny grass leaf and annular aluminum phosphate and controllable preparation method thereof, it is related to aluminum phosphate material technical field, comprising the following steps: S1.glass substrate is sequentially through lye, acid cleaning, then on its surface spray citric acid aqueous solution and carry out drying treatment;S2.preparation plating solution, using aluminum lactate and phosphoric acid as aluminum phosphate raw material, deionized water is solvent, and add diglycerol;S3.through spin coating method plating solution is placed on substrate, then, carry out self-assembly;S4.complete controllable preparation by different high-temperature heat treatment;S5.full fluorine polyether solution is evenly sprayed to product surface, carries out hydrophobization treatment.The application is first by constructing copper penny grass leaf and annular aluminum phosphate structure, then carries out hydrophobization treatment, and two kinds of aluminum phosphate structures both have very excellent hydrophobic property.In addition, the whole technological process of the application is simple, easy to large-scale industrial production.

Description

Technical Field

[0001] This invention relates to the field of aluminum phosphate materials technology, specifically to a thin film for substrate surface functionalization or modification, and more specifically, to a cyclic aluminum phosphate resembling a copper pennywort leaf and its controllable preparation method. Background Technology

[0002] Over millions of years of evolution, organisms in nature have developed numerous unique structures to adapt to their environments. For example, the special micro- and nano-scale protrusions on the surface of lotus leaves enable them to remain spotless; the unique structure of Norfolk Island pine leaves allows for the directional and controllable transport of liquids. Therefore, learning from nature and constructing the microstructures of materials can achieve special functions. Aluminum phosphate materials possess unique Al-O and PO tetrahedral structures. In the field of molecular sieves, scientists have prepared hundreds of aluminum phosphate materials with different pore structures. However, research reports on surface microstructures are relatively few. It is necessary to study a method for controllably preparing aluminum phosphate materials with surface micro- and nano-structures. Summary of the Invention

[0003] The purpose of this invention is to provide a copper coin grass leaf-like material and a cyclic aluminum phosphate and a controllable preparation method thereof. This method can controllably prepare aluminum phosphate with two structures by adjusting the process and formula, and can achieve excellent hydrophobic effect after hydrophobic treatment.

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

[0005] A controllable preparation method of pennywort leaves and cyclic aluminum phosphate includes the following steps:

[0006] S1. The glass substrate is cleaned with alkaline solution and acid solution in sequence to remove surface impurities. Then, a 2-5% citric acid aqueous solution is prepared and sprayed onto the cleaned glass surface. The substrate is then dried until there are no water stains.

[0007] Furthermore, during the drying process, maintain the temperature at around room temperature and avoid high-temperature heat treatment; to improve efficiency, the sample can be placed in a vacuum drying oven and dried quickly by vacuuming.

[0008] S2. Prepare the coating solution by using aluminum lactate and phosphoric acid as aluminum phosphate raw materials, deionized water as solvent, and adding diglycerides. The volume ratio of diglycerides to water is 1:30 to 1:40.

[0009] Furthermore, the amounts of aluminum lactate and phosphoric acid used meet the following ratios: the molar ratio of Al to P is 1:1; the concentration of Al in the aluminum phosphate coating solution is 0.01–0.1 mol / L.

[0010] Furthermore, to obtain a ring structure, a small amount of nitric acid can be added to the coating solution, with the molar ratio of nitric acid to phosphoric acid being 1:5 to 1:10.

[0011] S3. The coating solution is placed on the substrate by spin coating, and then self-assembly is performed.

[0012] Furthermore, the self-assembly conditions are as follows: while keeping the coated side facing down, the angle between the glass and the ground is maintained at 0-30°; during the drying process, the temperature is maintained at 20-30℃, the humidity is maintained at 20%-80%, and the self-assembly time is 3-5 minutes.

[0013] S4. Perform different high-temperature heat treatments to complete the controllable equipment. The specific operations are as follows:

[0014] To obtain the aluminum phosphate structure that mimics the leaves of *Hydrocotyle vulgaris*, the heating rate should not exceed 10℃ / min, the heat treatment temperature should be 300-500℃, and the heat treatment time should be 0.5-4h.

[0015] To obtain a cyclic aluminum phosphate structure, the heating rate should be no less than 10℃ / min, the heat treatment temperature should be 300-500℃, and the heat treatment time should be 0.5-4h.

[0016] To obtain the cyclic aluminum phosphate structure, a two-step high-temperature heat treatment can also be used. The self-assembled product is placed on a 200°C heating plate and maintained for no less than 20 minutes. Then it is heated to 300-500°C at a heating rate of no less than 10°C / min, and the heat treatment time is 0.5-4 hours.

[0017] S5. Spray the perfluoropolyether solution evenly onto the surface of the product to perform hydrophobic treatment.

[0018] The beneficial effects of this invention are:

[0019] This invention first constructs structures resembling pennywort leaves and ring-shaped aluminum phosphate, and then performs hydrophobic treatment, resulting in both aluminum phosphate structures exhibiting excellent hydrophobic properties. Furthermore, the entire process of this invention is simple and easily scalable for large-scale industrial production. Attached Figure Description

[0020] The invention will now be further described with reference to the accompanying drawings.

[0021] Figure 1 These are optical photographs of Embodiment 1 of the present invention;

[0022] Figure 2 This is a water contact angle test diagram from Embodiment 1 of the present invention;

[0023] Figure 3 These are optical photographs of Embodiment 2 of the present invention;

[0024] Figure 4This is a water contact angle test diagram from Embodiment 2 of the present invention;

[0025] Figure 5 These are optical photographs of Embodiment 3 of the present invention;

[0026] Figure 6 This is a water contact angle test diagram from Embodiment 3 of the present invention;

[0027] Figure 7 This is an optical photograph of Embodiment 4 of the present invention;

[0028] Figure 8 This is a water contact angle test diagram from Embodiment 4 of the present invention;

[0029] Figure 9 These are optical photographs of Embodiment 5 of the present invention;

[0030] Figure 10 This is a water contact angle test diagram from Embodiment 5 of the present invention;

[0031] Figure 11 This is a water contact angle test diagram after the glass substrate has been directly hydrophobically treated. Detailed Implementation

[0032] 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.

[0033] Example 1

[0034] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities; a 3% citric acid aqueous solution is prepared and sprayed onto the cleaned glass surface, and then dried until there are no water stains.

[0035] S2. Prepare the coating solution by accurately weighing aluminum lactate and adding it to the prepared deionized water. After stirring and dissolving, add phosphoric acid with an Al concentration of 0.01 mol / L and a molar ratio of Al to P of 1:1. Add diglycerol with a volume ratio of diglycerol to water of 1:40.

[0036] S3. Place the glass substrate with the uncoated side (not coated with citric acid solution) onto the spin coater suction cup. After adding the coating solution, spin coat at 800 rpm / min for 5 seconds. Place the coated side down on the sample holder, maintaining a 0° angle between the glass and the ground. Maintain a drying temperature of 25°C and a humidity of 20% in the drying chamber for 5 minutes.

[0037] S4. Place the sample in a muffle furnace for high-temperature heat treatment at a heating rate of 8℃ / min, a heat treatment temperature of 400℃, and a heat treatment time of 0.5h. Allow it to cool naturally to room temperature.

[0038] S5. Spray the perfluoropolyether solution evenly onto the sample surface, keeping the distance between the spray gun and the sample surface at 10cm. After drying for 30 minutes, repeat the above spraying once to ensure that the perfluoropolyether is evenly and completely covered, thus obtaining sample 1. Figure 1 and Figure 2 These are, respectively, an optical photograph and a water contact angle test diagram of Embodiment 1 of the present invention.

[0039] Example 2

[0040] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities; a 5% citric acid aqueous solution is prepared and sprayed onto the cleaned glass surface, and then dried until there are no water stains.

[0041] S2. Prepare the coating solution. Accurately weigh aluminum lactate and add it to the prepared deionized water. After stirring and dissolving, add phosphoric acid. The concentration of Al is 0.1 mol / L, and the molar ratio of Al to P is 1:1. Add diglycerol, with a volume ratio of diglycerol to water of 1:30. Add a small amount of nitric acid to the coating solution, with a molar ratio of nitric acid to phosphoric acid of 1:5.

[0042] S3. Place the glass substrate with the uncoated side (not coated with citric acid solution) onto the spin coater suction cup. After adding the coating solution, spin coat at 800 rpm / min for 5 seconds. Place the coated side down on the sample holder, maintaining a 30° angle between the glass and the ground. Maintain a drying temperature of 25°C and a humidity of 30% in the drying chamber for 3 minutes.

[0043] S4. Perform high-temperature heat treatment. Place the sample on a 200℃ heating plate and maintain for 20 minutes. Then heat to 300℃ at a heating rate of 15℃ / min for 0.5 hours. Allow it to cool naturally to room temperature.

[0044] S5. Spray the perfluoropolyether solution evenly onto the sample surface, keeping the distance between the spray gun and the sample surface at 10cm. After drying for 30 minutes, repeat the above spraying once to ensure that the perfluoropolyether is evenly and completely covered, thus obtaining sample 2. Figure 3 and Figure 4 These are, respectively, an optical photograph and a water contact angle test diagram of Embodiment 2 of the present invention.

[0045] Example 3

[0046] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities; a 3% citric acid aqueous solution is prepared and sprayed onto the cleaned glass surface, and then dried until there are no water stains.

[0047] S2. Prepare the coating solution. Accurately weigh aluminum lactate and add it to the prepared deionized water. After stirring and dissolving, add phosphoric acid. The concentration of Al is 0.05 mol / L, and the molar ratio of Al to P is 1:1. Add diglycerol, with a volume ratio of diglycerol to water of 1:30. Add a small amount of nitric acid to the coating solution, with a molar ratio of nitric acid to phosphoric acid of 1:5.

[0048] S3. Place the glass substrate with the uncoated side (not coated with citric acid solution) onto the spin coater suction cup. After adding the coating solution, spin coat at 800 rpm / min for 5 seconds. Place the coated side down on the sample holder, maintaining a 30° angle between the glass and the ground. Maintain the temperature at 25°C and the humidity at 50% in the drying chamber for 5 minutes.

[0049] S4. Perform high-temperature heat treatment, heat the sample to 300℃, with a heating rate of 15℃ / min, and heat treatment time of 0.5h, then allow it to cool naturally to room temperature.

[0050] S5. Spray the perfluoropolyether solution evenly onto the sample surface, keeping the distance between the spray gun and the sample surface at 10cm. After drying for 30 minutes, repeat the above spraying once to ensure that the perfluoropolyether is evenly and completely covered, thus obtaining sample 3. Figure 5 and Figure 6 These are, respectively, an optical photograph and a water contact angle test diagram of Embodiment 3 of the present invention.

[0051] Example 4

[0052] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities; a 3% citric acid aqueous solution is prepared and sprayed onto the cleaned glass surface, and then dried until there are no water stains.

[0053] S2. Prepare the coating solution. Accurately weigh aluminum lactate and add it to the prepared deionized water. After stirring and dissolving, add phosphoric acid. The concentration of Al is 0.05 mol / L, and the molar ratio of Al to P is 1:1. Add diglycerol, with a volume ratio of diglycerol to water of 1:30. Add a small amount of nitric acid to the coating solution, with a molar ratio of nitric acid to phosphoric acid of 1:5.

[0054] S3. Place the glass substrate with the uncoated side (not coated with citric acid solution) onto the spin coater suction cup. After adding the coating solution, spin coat at 800 rpm / min for 5 seconds. Place the coated side down on the sample holder, maintaining a 30° angle between the glass and the ground. Maintain the temperature at 25°C and the humidity at 80% in the drying chamber for 5 minutes.

[0055] S4. Perform high-temperature heat treatment, heat the sample to 300℃, with a heating rate of 15℃ / min, and heat treatment time of 0.5h, then allow it to cool naturally to room temperature.

[0056] S5. Spray the perfluoropolyether solution evenly onto the sample surface, keeping the distance between the spray gun and the sample surface at 10cm. After drying for 30 minutes, repeat the above spraying once to ensure that the perfluoropolyether is evenly and completely covered, thus obtaining sample 4. Figure 7 and Figure 8 These are, respectively, an optical photograph and a water contact angle test diagram from Embodiment 4 of the present invention.

[0057] Example 5

[0058] S1. The glass substrate is cleaned sequentially with alkaline solution and acid solution to remove surface impurities; a 4% citric acid aqueous solution is prepared and sprayed onto the cleaned glass surface, and then dried until there are no water stains.

[0059] S2. Prepare the coating solution. Accurately weigh aluminum lactate and add it to the prepared deionized water. After stirring and dissolving, add phosphoric acid. The concentration of Al is 0.01 mol / L, and the molar ratio of Al to P is 1:1. Add diglycerol, with a volume ratio of diglycerol to water of 1:30. Add a small amount of nitric acid to the coating solution, with a molar ratio of nitric acid to phosphoric acid of 1:10.

[0060] S3. Place the glass substrate with the uncoated side (not coated with citric acid solution) onto the spin coater suction cup. After adding the coating solution, spin coat at 800 rpm / min for 5 seconds. Place the coated side down on the sample holder, maintaining a 0° angle between the glass and the ground. Maintain a drying temperature of 25°C and a humidity of 30% in the drying chamber for 3 minutes.

[0061] S4. Perform high-temperature heat treatment. Place the sample on a 200℃ heating plate and maintain for 30 minutes, then heat to 450℃ at a heating rate of 15℃ / min for 4 hours.

[0062] S5. Spray the perfluoropolyether solution evenly onto the sample surface, keeping the distance between the spray gun and the sample surface at 10cm. After drying for 30 minutes, repeat the above spraying once to ensure that the perfluoropolyether is evenly and completely covered, thus obtaining sample 5. Figure 9 and Figure 10These are, respectively, an optical photograph and a water contact angle test diagram of Embodiment 5 of the present invention.

[0063] Table 1 shows the water contact angles of each sample after hydrophobication treatment. The comparative data in the table are the water contact angles of the glass substrates after direct hydrophobication treatment, compared with... Figure 11 Correspondingly, the hydrophobication step uses S5.

[0064] Table 1

[0065]

[0066] 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 process for the controlled preparation of a leaf of a plant of the genus Pogostemon and a ring of aluminum orthophosphate, characterized in that, The method comprises the following steps: S1. The glass substrate is sequentially cleaned by alkali solution and acid solution to remove surface impurities, then a 2-5% citric acid aqueous solution is sprayed on the surface of the glass substrate, and drying treatment is performed until no water stains are present; S2. A coating solution is prepared, aluminum lactate and phosphoric acid are used as aluminum phosphate raw materials, deionized water is used as a solvent, and diglycerol is added, and the volume ratio of diglycerol to water is 1:30-1:40; Nitric acid is added to the coating solution, and the molar ratio of the amount of nitric acid to the amount of phosphoric acid is controlled to be 1:5-1:10, so that a ring structure can be obtained; S3. The coating solution is placed on the substrate by spin coating, and then self-assembly is performed; S4. Controlled preparation is completed by different high-temperature heat treatment; The heating rate is controlled to be not higher than 10℃ / min, the heat treatment temperature is 300-500℃, the heat treatment time is 0.5-4h, and an imitation copper money grass leaf aluminum phosphate structure is obtained; Two-step high-temperature heat treatment is adopted, the self-assembled product is placed on a 200℃ heating plate for not less than 20min, then heated to 300-500℃ at a rate of not less than 10℃ / min, and the heat treatment time is 0.5-4h, so that a ring-shaped aluminum phosphate structure is obtained; S5. The perfluoropolyether solution is uniformly sprayed on the surface of the product for hydrophobic treatment.

2. A process for the controlled preparation of a leaf of Veronica cuprina and ring-shaped aluminum phosphate according to claim 1, characterized in that, The drying process is carried out at room temperature.

3. A process for the controlled preparation of a leaf of a plant of the genus Hyptis and a ring of aluminum orthophosphate according to claim 1, characterized in that, The drying treatment is: placed in a vacuum drying oven, and dried quickly by vacuumizing.

4. A process for the controlled preparation of a leaf of Veronica cuprina and ring-shaped aluminum phosphate according to claim 1, characterized in that, The amounts of the aluminum lactate and the phosphoric acid satisfy the following ratio: the molar ratio of Al element to P element is 1:1; the concentration of Al in the aluminum phosphate coating solution is 0.01-0.1mol / L.

5. A process for the controlled preparation of a leaf of a plant of the genus Hyptis and a ring of aluminum orthophosphate according to claim 1, characterized in that, The self-assembly conditions are: the coating surface is kept downward, the angle between the glass and the ground is maintained at 0-30°; during the drying process, the temperature is maintained at 20-30℃, the humidity is maintained at 20%-80%, and the self-assembly time is 3-5min.

6. A type of pennywort leaf and cyclic aluminum phosphate, characterized in that, Prepared according to the preparation method of any one of claims 1-5. Prepared according to the preparation method of any one of claims 1-5.

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