A high-strength nano-ceramic metal plate and its preparation method

Abstract

The present invention relates to the field of building curtain wall technology and discloses a high-strength nano-ceramic metal plate and a preparation method thereof. A metal plate substrate is used as an anode and a conductive material is used as a cathode. The anode and cathode are simultaneously inserted into a mixed solution containing a methacrylate and a fluorocarbon surfactant and connected to a DC power supply to modify the metal plate substrate. A porcelain layer is then coated on the modified metal plate. The metal plate coated with the porcelain layer is cured at 150 to 280°C, and the high-strength nano-ceramic metal plate is obtained after cooling. The present invention forms a polymer on the surface and pores / crevices of the metal plate substrate through the anode modification method, which protects and fills the pores or cracks on the surface of the metal plate substrate, thereby improving the strength of the metal plate substrate. Furthermore, the polymer on the surface of the metal plate substrate carries a layer of carboxylate ions, which helps to form a network of silicon-oxygen and aluminum-oxygen bonds with silicon and aluminum in the porcelain layer material, thereby improving the adhesion of the porcelain layer to the metal plate substrate.

Description

Technical Field

[0001] The invention relates to the technical field of building curtain walls and discloses a high-strength nano-porcelain metal plate and a preparation method thereof. Background Art

[0002] Porcelain-baked metal panels are curtain wall decorative panels formed by spraying an inorganic water-based ceramic coating onto a metal substrate and then curing it. They are heat-resistant, non-flammable, smoke-free, highly hard, easy to clean, safe, environmentally friendly, and energy-efficient. In recent years, they have become increasingly popular in public places such as subway stations, tunnels, high-speed rail stations, airports, hospitals, and schools. However, the substrate used to process the porcelain-baked metal panels may have defects such as cracks and pores, and existing porcelain-baked metal panels also have a relatively low adhesion to the porcelain material. In the prior art, pre-treatment processes such as sandblasting are often used to treat the metal substrate before processing the porcelain-baked metal panels. This increases the contact area between the porcelain layer and the substrate, thereby increasing the adhesion between the porcelain layer and the substrate. However, this further deepens the growth of cracks or pores on the substrate surface, adversely affecting the strength of the porcelain-baked metal panels. Summary of the Invention

[0003] The purpose of the present invention is to provide a high-strength nano-ceramic metal plate and its preparation method, which not only protects and fills the surface gaps or pores of the metal plate substrate, improves the strength of the metal plate substrate, but also helps to improve the adhesion between the porcelain layer and the metal plate substrate.

[0004] In order to achieve the above technical effects, the technical solution adopted by the present invention is:

[0005] A method for preparing a high-strength nano-ceramic metal plate, comprising:

[0006] dissolving methacrylate in water, and adding a fluorocarbon surfactant to the methacrylate solution to form a mixed solution;

[0007] Using a metal plate substrate as an anode and a conductive material as a cathode, the anode and cathode are simultaneously inserted into the mixed solution and connected to a DC power supply for more than 20 minutes to obtain a modified metal plate;

[0008] Coating a porcelain layer on the modified metal plate, wherein the porcelain layer is mainly composed of a mixture of silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol, and water;

[0009] The metal plate coated with the porcelain layer is cured at 150-280° C., and then cooled to obtain a high-strength nano-porcelain metal plate.

[0010] Furthermore, the metal plate substrate is an aluminum plate, an aluminum alloy plate or a stainless steel plate.

[0011] Furthermore, the methacrylate is a combination of one or more of potassium methacrylate, sodium methacrylate, and zinc methacrylate, and the fluorocarbon surfactant is a cationic fluorocarbon surfactant or an amphoteric fluorocarbon surfactant; wherein the molar concentration of methacrylate in the mixed solution is 0.2 to 0.6 mol / L, and the molar concentration of the fluorocarbon surfactant in the mixed solution is 0.04 to 0.08 mol / L.

[0012] Furthermore, the current provided by the DC power supply is 2-6 mA.

[0013] Furthermore, the porcelain layer comprises, by weight, 2 to 6 parts of silicon dioxide powder, 0.2 to 3 parts of aluminum oxide powder, 25 to 40 parts of tetraethoxysilane, 25 to 40 parts of tetraisopropoxysilane, 36 to 60 parts of isopropyl alcohol, and 50 to 80 parts of water.

[0014] Furthermore, the step of coating a porcelain layer on the modified metal plate includes:

[0015] Premixing silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol, and water to form a first mixture;

[0016] The first mixture is kept at 80±5°C for 2 to 10 hours, isopropyl alcohol is added to dilute the first mixture, and the mixture is stirred evenly to form a ceramic layer coating;

[0017] The coating is coated on the modified metal plate by spin coating or spray coating.

[0018] In order to achieve the above technical effects, the present invention also provides a high-strength nano-ceramic metal plate, comprising:

[0019] A modified metal plate substrate, wherein the modified metal plate substrate is obtained by using a metal plate as an anode material and performing electrical modification in a mixed solution containing methacrylate and a fluorocarbon surfactant;

[0020] The porcelain layer is mainly formed by mixing silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol and water, and is obtained by heat preservation and curing at 150-280°C.

[0021] The metal plate substrate is an aluminum plate, an aluminum alloy plate or a stainless steel plate.

[0022] Furthermore, the methacrylate is a combination of one or more of potassium methacrylate, sodium methacrylate, and zinc methacrylate, and the fluorocarbon surfactant is a cationic fluorocarbon surfactant or an amphoteric fluorocarbon surfactant; wherein the molar concentration of methacrylate in the mixed solution is 0.2 to 0.6 mol / L, and the molar concentration of the fluorocarbon surfactant in the mixed solution is 0.04 to 0.08 mol / L.

[0023] Furthermore, the porcelain layer includes 2 to 6 parts of silicon dioxide powder, 0.2 to 3 parts of aluminum oxide powder, 25 to 40 parts of tetraethoxysilane, 25 to 40 parts of tetraisopropoxysilane, 36 to 60 parts of isopropyl alcohol, and 50 to 80 parts of water.

[0024] Compared with the existing technology, the beneficial effects of the present invention are: the present invention forms a polymer on the surface and pores / crevices of the metal plate substrate through the method of anodic modification, which plays a role in protecting and filling the gaps or pores on the surface of the metal plate substrate, thereby improving the strength of the metal plate substrate; and the polymer on the surface of the metal plate substrate carries a layer of carboxylate ions, which helps to form a network structure of silicon-oxygen bonds and aluminum-oxygen bonds with silicon and aluminum in the porcelain layer material, thereby improving the adhesion between the porcelain layer and the metal plate substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a flow chart of the preparation method of the high-strength nano-ceramic metal plate in Example 1 or 2. DETAILED DESCRIPTION

[0026] The present invention will be described in further detail below with reference to the embodiments and accompanying drawings. However, this should not be construed as limiting the scope of the present invention to the following embodiments, as all technologies implemented based on the present invention fall within the scope of the present invention.

[0027] Example 1

[0028] See also Figure 1 , a method for preparing a high-strength nano-ceramic metal plate, comprising:

[0029] dissolving methacrylate in water, and adding a fluorocarbon surfactant to the methacrylate solution to form a mixed solution;

[0030] Using a metal plate substrate as an anode and a conductive material as a cathode, the anode and cathode are simultaneously inserted into the mixed solution and connected to a DC power supply for more than 20 minutes to obtain a modified metal plate;

[0031] Coating a porcelain layer on the modified metal plate, wherein the porcelain layer is mainly composed of a mixture of silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol, and water;

[0032] The metal plate coated with the porcelain layer is cured at 150-280° C., and then cooled to obtain a high-strength nano-porcelain metal plate.

[0033] In this embodiment, a metal plate substrate is used as the anode material and a conductive material is used as the cathode material. After the anode material and the cathode material are simultaneously immersed in a mixed solution containing methacrylate and fluorocarbon surfactant and energized, the metal plate substrate of the anode is positively charged, which can attract methacrylate ions and fluorocarbon groups to move toward the anode, not only allowing the methacrylate ions and fluorocarbon groups to adhere to the surface of the metal plate substrate, but also allowing the methacrylate ions to penetrate into the surface gaps or pores of the metal plate substrate under the action of charge attraction. When the power is continuously applied, the cathode generates The electrons also continue to move toward the anode through the solution, bombarding the methacrylate ions attached to the surface of the metal plate substrate and infiltrated into the gaps or pores, causing the carbon-carbon double bonds in the methacrylate to break, and polymerize with each other on the surface of the metal plate substrate and in the pores / gaps to form polymers, which play a role in protecting and filling the gaps or pores on the surface of the metal plate substrate and improving the strength of the metal plate substrate; the polymer on the surface of the metal plate substrate carries a layer of carboxylate ions, which helps to form a network structure of silicon-oxygen bonds and aluminum-oxygen bonds with silicon and aluminum in the porcelain layer material, thereby improving the adhesion between the porcelain layer and the metal plate substrate. In addition, the fluorocarbon surfactant in the mixed solution can not only improve the wettability of methacrylate ions on the surface of the metal plate, allowing the methacrylate ions to contact the surface of the metal plate and increase the adhesion area of ​​the methacrylate ions to the metal plate; in addition, the radius of the fluorine ions in the fluorocarbon organic matter is small, and after being attracted by the anode metal plate, the fluorine ions can better penetrate under the surface of the metal plate, and under the action of the strong electronegativity of the fluorine ions, the organic groups on the exposed metal surface are positively charged, which can enhance the binding ability of the fluorocarbon organic compound and the methacrylate ions, thereby further enhancing the adhesion between the porcelain layer and the metal plate substrate, and the free fluorine ions in the mixed solution can act as halogen elements to promote the breaking of carbon-carbon double bonds, which further promotes the polymerization of methacrylate ions on the surface of the metal plate substrate and in the pores / crevices to form polymers.

[0034] Based on the same inventive concept, this embodiment also provides a high-strength nano-ceramic metal plate, comprising:

[0035] A modified metal plate substrate, wherein the modified metal plate substrate is obtained by using a metal plate as an anode material and performing electrical modification in a mixed solution containing methacrylate and a fluorocarbon surfactant;

[0036] The porcelain layer is mainly formed by mixing silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol and water, and is obtained by heat preservation and curing at 150-280°C.

[0037] The metal plate substrate in this embodiment is an aluminum plate, an aluminum alloy plate or a stainless steel plate.

[0038] The methacrylate is a combination of one or more of potassium methacrylate, sodium methacrylate, and zinc methacrylate, and the fluorocarbon surfactant is a cationic fluorocarbon surfactant or an amphoteric fluorocarbon surfactant.

[0039] In order to ensure that the polymer on the surface of the metal plate substrate can be stably formed, the current provided by the DC power supply is controlled to be 2-6 mA in this embodiment.

[0040] Example 2

[0041] See also Figure 1 , a method for preparing a high-strength nano-ceramic metal plate, comprising:

[0042] Step 1, dissolving methacrylate in water, and adding a fluorocarbon surfactant to the methacrylate solution to form a mixed solution;

[0043] In this embodiment, a mixed solution is prepared using sodium methacrylate and a quaternary ammonium cationic fluorocarbon surfactant as raw materials. The molar concentration of methacrylate in the prepared mixed solution is 0.3 mol / L, and the molar concentration of the fluorocarbon surfactant is 0.05 mol / L.

[0044] Step 2: Using a 2.0 mm thick aluminum alloy plate substrate as the anode and a carbon rod as the cathode, the anode and cathode were simultaneously inserted into the mixed solution and connected to a DC power supply for 120 minutes to obtain a modified metal plate; in this embodiment, the current provided by the DC power supply was 5 mA.

[0045] Step 3: Premix 4 parts of silicon dioxide powder, 1.5 parts of aluminum oxide powder, 30 parts of tetraethoxysilane, 30 parts of tetraisopropoxysilane, 15 parts of isopropyl alcohol, and 55 parts of water to form a first mixture;

[0046] Step 4: After the first mixture is kept at 80±5°C for 8 hours, 30 parts of isopropyl alcohol is added to the first mixture and stirred to form a ceramic coating;

[0047] Step 5: Apply the coating to the modified metal plate by spraying; in this embodiment, the spraying thickness is controlled to be 0.05-0.12 mm;

[0048] Step 6: Curing the metal plate coated with the porcelain layer at 150-280° C., and obtaining a high-strength nano-ceramic metal plate after cooling.

[0049] In this example, an aluminum alloy plate substrate of the same model and size was directly prepared using the method of steps 3 to 6 to obtain a comparative sample for performance comparison with the high-strength nano-ceramic metal plate prepared using steps 1 to 6. The test items were:

[0050] Thickness of porcelain layer: Measure in accordance with the provisions of GB / T4957. The local film thickness at least at five locations including the four corners and the center of each sample shall be measured.

[0051] Tensile strength: Measure according to the tensile strength test procedures for thin plate specimens with a thickness of 0.1 to 3 mm in Appendix B of GB / T228.1.

[0052] Impact resistance: The test is carried out in accordance with the provisions of GB / T1732. The weight of the impact hammer is 1000g±1g, the punch diameter is 15.9mm±0.3mm, the porcelain decorative surface of the specimen faces upwards, and the maximum impact height at which no cracks, wrinkles or peeling of the porcelain decorative surface are observed is measured.

[0053] Dry Adhesion: Conduct a cross-hatch test according to GB / T9286, with a 1mm spacing between the cross-hatch patterns. Place a 25mm wide tape with an adhesive strength of (10±1)N / 25mm over the cross-hatch pattern. Remove any air from under the tape and quickly pull it vertically apart. Observe the pattern using an AM413ZT digital microscope at 200x magnification, and observe the degree of porcelain shedding at each grid.

[0054] The relevant test data of the high-strength nano-ceramic metal plate prepared in this embodiment and the comparative sample are shown in Table 1 below:

[0055] Table 1 Comparison of performance data of porcelain-fused-to-metal plate samples

[0056]

[0057] The above-mentioned relevant test data show that the tensile strength and impact resistance of the high-strength nano-ceramic metal plate made of anodically modified aluminum alloy plate are improved, and the adhesion between the porcelain layer and the substrate is also significantly improved.

[0058] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a high-strength nano-ceramic metal plate, characterized in that: include: dissolving methacrylate in water, and adding a fluorocarbon surfactant to the methacrylate solution to form a mixed solution; wherein the molar concentration of methacrylate in the mixed solution is 0.2 to 0.6 mol / L, and the molar concentration of the fluorocarbon surfactant in the mixed solution is 0.04 to 0.08 mol / L; Using a metal plate substrate as an anode and a conductive material as a cathode, the anode and cathode are simultaneously inserted into the mixed solution and connected to a DC power supply for more than 20 minutes to obtain a modified metal plate; the DC power supply provides a current of 2 to 6 mA; Coating a porcelain layer on the modified metal plate, wherein the porcelain layer is mainly composed of a mixture of silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol, and water; The metal plate coated with the porcelain layer is cured at 150-280° C., and then cooled to obtain a high-strength nano-porcelain metal plate.

2. The method for preparing a high-strength nano-ceramic metal plate according to claim 1, characterized in that: The metal plate substrate is an aluminum plate, an aluminum alloy plate or a stainless steel plate.

3. The method for preparing a high-strength nano-ceramic metal plate according to claim 1, characterized in that: The methacrylate is a combination of one or more of potassium methacrylate, sodium methacrylate, and zinc methacrylate, and the fluorocarbon surfactant is a cationic fluorocarbon surfactant or an amphoteric fluorocarbon surfactant.

4. The method for preparing a high-strength nano-ceramic metal plate according to claim 1, characterized in that: In parts by weight, the porcelain layer comprises 2 to 6 parts of silicon dioxide powder, 0.2 to 3 parts of aluminum oxide powder, 25 to 40 parts of tetraethoxysilane, 25 to 40 parts of tetraisopropoxysilane, 36 to 60 parts of isopropyl alcohol, and 50 to 80 parts of water.

5. The method for preparing a high-strength nano-ceramic metal plate according to claim 4, characterized in that: The steps of coating the ceramic layer on the modified metal plate include: Premixing silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol, and water to form a first mixture; The first mixture is kept at 80±5°C for 2 to 10 hours, isopropyl alcohol is added to dilute the first mixture, and the mixture is stirred evenly to form a ceramic layer coating; The coating is coated on the modified metal plate by spin coating or spray coating.

6. A high-strength nano-ceramic metal plate, characterized in that: include: A modified metal plate substrate, wherein the modified metal plate substrate is obtained by using a metal plate as an anode material and performing electrical modification in a mixed solution containing methacrylate and a fluorocarbon surfactant; The molar concentration of methacrylate in the mixed solution is 0.2 to 0.6 mol / L, and the molar concentration of the fluorocarbon surfactant in the mixed solution is 0.04 to 0.08 mol / L. The electrical modification comprises inserting the metal plate substrate as an anode and the conductive material as a cathode simultaneously into the mixed solution and connecting a DC power supply for more than 20 minutes to obtain a modified metal plate. The current provided by the DC power supply is 2 to 6 mA. The porcelain layer is mainly formed by mixing silicon dioxide powder, aluminum oxide powder, tetraethoxysilane, tetraisopropoxysilane, isopropyl alcohol and water, and is obtained by heat preservation and curing at 150-280°C; The metal plate substrate is an aluminum plate, an aluminum alloy plate or a stainless steel plate.

7. The high-strength nano-ceramic metal plate according to claim 6, characterized in that: The methacrylate is a combination of one or more of potassium methacrylate, sodium methacrylate, and zinc methacrylate, and the fluorocarbon surfactant is a cationic fluorocarbon surfactant or an amphoteric fluorocarbon surfactant.

8. The high-strength nano-ceramic metal plate according to claim 6, characterized in that: The porcelain layer comprises 2-6 parts of silicon dioxide powder, 0.2-3 parts of aluminum oxide powder, 25-40 parts of tetraethoxysilane, 25-40 parts of tetraisopropoxysilane, 36-60 parts of isopropyl alcohol and 50-80 parts of water.

Images