Preparation method of full-coverage high-precision graphene composite nano ceramic coating

Abstract

The invention provides a preparation method of a full-coverage high-precision graphene composite nano ceramic coating, and belongs to the technical field of ceramic coating preparation. The method comprises the following steps: performing magnetization pretreatment on a workpiece to obtain a pretreated workpiece; then the pretreated workpiece is placed in a nano-deposition solution for liquid-phase nano-deposition, and a workpiece with a deposited nano-composite ceramic coating is obtained; and finally, the workpiece deposited with the composite ceramic coating is subjected to impurity removal treatment and vapor phase nanometer deposition, and a graphene composite nanometer ceramic coating workpiece is obtained. Wherein the liquid-phase nano-deposition comprises a first liquid-phase nano-deposition, a second liquid-phase nano-deposition and a third liquid-phase nano-deposition. By adopting gradient magnetic field force control, the precision of the prepared graphene composite nano ceramic coating can be improved, and the optimal tolerance of the thickness of the coating in the range of per square meter is within + / -3 microns.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic coating preparation, and in particular to a method for preparing a fully covered high-precision graphene composite nano-ceramic coating. Background Art

[0002] In the existing nano-coating preparation technology, the uniformity and thickness control of the coating is a key problem. Although traditional coating preparation methods such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) can achieve a certain degree of uniformity, they have great limitations in high-precision thickness control, especially on large-area complex structural substrates. It is almost impossible to achieve a thickness tolerance of ±3μm. In addition, the existing technology is difficult to achieve full coverage of complex-shaped substrates, and it is easy to produce dead corners, resulting in uneven coating performance.

[0003] At present, electromagnetic deposition cannot achieve precise control of coating thickness, and it is difficult to achieve full coverage of complex-shaped substrates. Therefore, it is of great significance to study a preparation method of graphene composite nano-ceramic coating and achieve high-precision control of coating thickness. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a full-coverage high-precision graphene composite nano-ceramic coating to solve the problem of large coating thickness tolerance in the prior art.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a fully covered high-precision graphene composite nano-ceramic coating, comprising the following steps:

[0007] (1) performing magnetization pretreatment on the workpiece to obtain a pretreated workpiece;

[0008] (2) placing the pretreated workpiece in a nano-deposition liquid for liquid phase nano-deposition to obtain a workpiece with a deposited nano-composite ceramic coating;

[0009] (3) performing impurity removal treatment and vapor phase nano-deposition on the workpiece on which the composite ceramic coating is deposited to obtain a graphene composite nano-ceramic coating workpiece;

[0010] The liquid phase nano-deposition comprises a first liquid phase nano-deposition, a second liquid phase nano-deposition and a third liquid phase nano-deposition.

[0011] Preferably, in the step (1), the magnetization voltage of the magnetization pretreatment is 100 to 1800 V, and the magnetization time is 1 to 10 s.

[0012] Preferably, in the step (2), the raw materials of the nano-deposition liquid include the following components in parts by weight: 0.5-5 parts of graphene, 0.1-3 parts of carbon nanotubes, 1.8-18.6 parts of nano-silicon dioxide, 0.5-5 parts of nano-aluminum oxide, 0.5-1.5 parts of nano-zirconium oxide, 0.5-5.6 parts of magneto-ionic composite agent, 0.1-2.8 parts of ion regulator, 0.1-4.2 parts of ion cross-linking agent, 0.01-2.2 parts of nano-dispersant, 0.1-3.2 parts of aqueous stabilizer, and 15-55 parts of deionized water.

[0013] Preferably, the preparation method of the nano-deposition liquid is: dispersing graphene, carbon nanotubes, nano-silicon dioxide, nano-aluminum oxide and nano-zirconium oxide in deionized water, adding a silane coupling agent for modification, and then adding a magneto-electric ion complex, an ion regulator, an ion cross-linking agent, a nano-dispersant and an aqueous stabilizer, stirring evenly and then ripening.

[0014] Preferably, the magneto-ionic complex comprises [bmim]FeCl 4 、[bpy]FeCl 4 、[bmp]FeCl 4 and [pbmim](FeCl 4 ) 2 One or more of the .

[0015] Preferably, the magnetic field force during the first liquid phase nano-deposition is 10-30N, and the deposition time is 0.1-1.0h; the magnetic field force during the second liquid phase nano-deposition is 50-150N, and the deposition time is 0.1-1h; the magnetic field force during the third liquid phase nano-deposition is 200-400N, and the deposition time is 0.1-1h.

[0016] Preferably, the magnetic field force during the impurity removal treatment is 100-500N and the time is 6-60min.

[0017] Preferably, the magnetic field force during the gas phase nano-deposition is 100-500N and the time is 0.5-8h.

[0018] Beneficial effects of the present invention:

[0019] (1) The present invention adopts gradient magnetic field force control to improve the precision of the prepared graphene composite nano-ceramic coating, so that the thickness tolerance of the coating per square meter is optimized to within ±3 μm.

[0020] (2) The gradient magnetic field force-controlled deposition method of the present invention, combined with the silane coupling agent modification in the nano-deposition liquid preparation process, can achieve dead-angle-free coating coverage of the workpiece. DETAILED DESCRIPTION

[0021] The present invention provides a method for preparing a fully covered high-precision graphene composite nano-ceramic coating, comprising the following steps:

[0022] (1) performing magnetization pretreatment on the workpiece to obtain a pretreated workpiece;

[0023] (2) placing the pretreated workpiece in a nano-deposition liquid for liquid phase nano-deposition to obtain a workpiece with a deposited nano-composite ceramic coating;

[0024] (3) performing impurity removal treatment and vapor phase nano-deposition on the workpiece on which the composite ceramic coating is deposited to obtain a graphene composite nano-ceramic coating workpiece;

[0025] The liquid phase nano-deposition comprises a first liquid phase nano-deposition, a second liquid phase nano-deposition and a third liquid phase nano-deposition.

[0026] In the present invention, in the step (1), the magnetization voltage of the magnetization pretreatment is 100-1800V, preferably 150-1500V, and more preferably 200-1000V; the magnetization time is 1-10s, preferably 2-8s, and more preferably 4-6s.

[0027] In the present invention, in the step (2), the raw materials of the nano-deposition liquid include the following components in parts by weight: 0.5-5 parts of graphene, 0.1-3 parts of carbon nanotubes, 1.8-18.6 parts of nano-silicon dioxide, 0.5-5 parts of nano-aluminum oxide, 0.5-1.5 parts of nano-zirconium oxide, 0.5-5.6 parts of magneto-ionic composite agent, 0.1-2.8 parts of ion regulator, 0.1-4.2 parts of ion cross-linking agent, 0.01-2.2 parts of nano-dispersant, 0.1-3.2 parts of aqueous stabilizer, and 15-55 parts of deionized water.

[0028] In the present invention, the preparation method of the nano-deposition liquid is: graphene, carbon nanotubes, nano-silicon dioxide, nano-aluminum oxide and nano-zirconium oxide are dispersed in deionized water, a silane coupling agent is added for modification, and then a magneto-electric ion complex, an ion regulator, an ion cross-linking agent, a nano-dispersant and an aqueous stabilizer are added, and the mixture is stirred evenly and then matured.

[0029] In the present invention, the added amount of the silane coupling agent is 3-5% of the total amount of graphene, carbon nanotubes, nano silicon dioxide, nano aluminum oxide and nano zirconium oxide, preferably 4%.

[0030] In the present invention, the modification is carried out under heating conditions when the pH value is 6 to 8, and ultrasonic treatment is carried out during the modification process, wherein the heating temperature is 40 to 50° C., the ultrasonic power is 80 to 120 W during the ultrasonic treatment, and the time is 0.1 to 1 h.

[0031] In the present invention, the magneto-ionic composite agent comprises [bmim]FeCl 4 、[bpy]FeCl 4 、[bmp]FeCl 4 and [pbmim](FeCl 4 ) 2 One or more of the .

[0032] In the present invention, the ion regulator is preferably tetrabutylammonium hydroxide, tetrabutylammonium chloride or dodecyltrimethylammonium chloride; the ion crosslinking agent is one or more of diethylene glycol dimethacrylate, triallyl cyanurate, di-tert-butyl peroxide and isopropylbenzene oxide; the nanodispersant comprises one or more of sodium polyacrylate, ammonium polyacrylate and sodium hexametaphosphate; the aqueous stabilizer comprises SILRES MP50E and / or HD-020.

[0033] In the present invention, the magnetic field force during the first liquid-phase nano-deposition is 10-30N, preferably 15-25N, more preferably 20N, and the deposition time is 0.1-1.0h, preferably 0.5h; the magnetic field force during the second liquid-phase nano-deposition is 50-150N, preferably 80-120N, more preferably 100N, and the deposition time is 0.1-1.0h, preferably 0.5h; the magnetic field force during the third liquid-phase nano-deposition is 200-400N, preferably 250-350N, more preferably 300N, and the deposition time is 0.1-1.0h, preferably 0.5h.

[0034] In the present invention, the magnetic field force during the impurity removal treatment is 100-500N, preferably 200-400N, more preferably 300N, and the time is 6-60min, preferably 10-50min, more preferably 30-40min.

[0035] In the present invention, the magnetic field force during the vapor phase nanodeposition is 100-500N, preferably 200-400N, more preferably 300N, and the time is 0.5-8h, preferably 2-6h, more preferably 3-5h.

[0036] The present invention prepares the graphene composite nano-ceramic coating by liquid phase deposition through gradient magnetic field force control, which can omit the step of rearrangement and densification and can also ensure the quality of the graphene composite nano-ceramic coating.

[0037] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0038] Example 1

[0039] 2 parts of graphene, 1.5 parts of carbon nanotubes, 15 parts of nano-silicon dioxide, 5 parts of nano-aluminum oxide and 1 part of nano-zirconium oxide were dispersed in 40 parts of deionized water, and then KH540 (4% addition) was added, and the pH value was adjusted to 8 with sodium hydroxide solution, and then heated to 40°C for modification. The power of ultrasound during the modification process was 100W, and the modification time was 0.5h. Then it was cooled to room temperature, and 3 parts of magnetic electric ion composite agent [bmim]FeCl were added. 4 , 1 part of ion regulator tetrabutylammonium hydroxide, 3 parts of ion crosslinking agent cumene oxide, 0.5 parts of nano-dispersant sodium hexametaphosphate, 1 part of aqueous stabilizer SILRES MP50E, stir evenly and let stand and mature for 5 hours to obtain a nano-deposition liquid, in which the particle size range of nano-silicon dioxide, nano-aluminum oxide and nano-zirconium oxide is 10-30nm.

[0040] The battery shell is magnetized pre-treated by using a magnetizer under the conditions of a magnetizing voltage of 200V and a magnetizing time of 5s to obtain a pre-treated battery shell; the pre-treated battery shell is placed in a nano-deposition liquid, and liquid phase nano-deposition is performed in sequence, and the specific process parameters are: the magnetic field force is 20N and the deposition time is 0.5h during the first liquid phase nano-deposition, the magnetic field force is 100N and the deposition time is 0.5h during the second liquid phase nano-deposition, and the magnetic field force is 300N and the deposition time is 0.5h during the third liquid phase nano-deposition, to obtain a battery shell with a deposited nano-composite ceramic coating; the battery shell with the deposited nano-composite ceramic coating is placed in deionized water, and is subjected to a de-impurity treatment for 30min under the condition of a magnetic field force of 300N, and finally, a gas phase nano-deposition is performed for 3h under the condition of a magnetic field force of 300N to obtain a graphene composite nano-ceramic coating battery shell.

[0041] Example 2

[0042] The difference from Example 1 is that the process parameters of liquid phase nanodeposition are different, specifically: the magnetic field force is 10N and the deposition time is 1h during the first liquid phase nanodeposition, the magnetic field force is 50N and the deposition time is 1h during the second liquid phase nanodeposition, and the magnetic field force is 200N and the deposition time is 0.1h during the third liquid phase nanodeposition, and other conditions are the same.

[0043] Example 3

[0044] The difference from Example 1 is that the process parameters of liquid phase nanodeposition are different, specifically: the magnetic field force is 30N and the deposition time is 0.1h during the first liquid phase nanodeposition, the magnetic field force is 150N and the deposition time is 0.1h during the second liquid phase nanodeposition, and the magnetic field force is 400N and the deposition time is 1h during the third liquid phase nanodeposition, and other conditions are the same.

[0045] Comparative Example 1

[0046] The difference from Example 1 is that the liquid phase nano-deposition adopts one-time liquid phase nano-deposition, and the process parameters are: the magnetic field force is 20N, and the deposition time is 1.5h.

[0047] Comparative Example 2

[0048] The difference from Example 1 is that no modification treatment is performed during the preparation of the nano-deposition liquid. Specifically, 2 parts of graphene, 1.5 parts of carbon nanotubes, 15 parts of nano-silicon dioxide, 5 parts of nano-aluminum oxide and 1 part of nano-zirconium oxide are dispersed in 40 parts of deionized water, and ultrasonic treatment is performed, wherein the ultrasonic power is 100 W, the time is 0.5 h, and then 3 parts of the magnetoelectric ion composite agent [bmim]FeCl 4 , 1 part of ion regulator tetrabutylammonium hydroxide, 3 parts of ion crosslinking agent cumene oxide, 0.5 parts of nano-dispersant sodium hexametaphosphate, 1 part of aqueous stabilizer SILRES MP50E, stir evenly and let stand and mature for 5 hours to obtain a nano-deposition liquid, in which the particle size range of nano-silicon dioxide, nano-aluminum oxide and nano-zirconium oxide is 10-30nm, and other conditions are the same.

[0049] The coating thickness of the graphene composite nano-ceramic coating battery shells prepared in Examples 1 to 3 and Comparative Examples 1 to 2 was measured by ultrasonic thickness measurement, and the thickness tolerance was obtained according to the test results. The results are shown in Table 1:

[0050] Table 1 Test results

[0051]

[0052] As can be seen from Table 1, the use of gradient magnetic field force control for liquid phase deposition is more conducive to controlling the uniformity of the coating, so that the thickness tolerance is controlled within ±3 μm, while also avoiding the appearance of uncoated dead corners on the workpiece surface.

[0053] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a fully covered high-precision graphene composite nano-ceramic coating, characterized in that: The steps include: (1) performing magnetization pretreatment on the workpiece to obtain a pretreated workpiece; (2) placing the pretreated workpiece in a nano-deposition liquid for liquid phase nano-deposition to obtain a workpiece with a deposited nano-composite ceramic coating; (3) performing impurity removal treatment and vapor phase nano-deposition on the workpiece on which the nano-composite ceramic coating is deposited to obtain a workpiece with a graphene composite nano-ceramic coating; The liquid phase nano-deposition comprises a first liquid phase nano-deposition, a second liquid phase nano-deposition and a third liquid phase nano-deposition.

2. The method for preparing a fully covered high-precision graphene composite nano-ceramic coating according to claim 1, characterized in that: In the step (1), the magnetization voltage of the magnetization pretreatment is 100 to 1800 V, and the magnetization time is 1 to 10 s.

3. The method for preparing the full coverage high-precision graphene composite nano-ceramic coating according to claim 1 or 2, characterized in that: In the step (2), the raw materials of the nano-deposition liquid include the following components in parts by weight: 0.5-5 parts of graphene, 0.1-3 parts of carbon nanotubes, 1.8-18.6 parts of nano-silicon dioxide, 0.5-5 parts of nano-aluminum oxide, 0.5-1.5 parts of nano-zirconium oxide, 0.5-5.6 parts of magneto-electric ion composite agent, 0.1-2.8 parts of ion regulator, 0.1-4.2 parts of ion cross-linking agent, 0.01-2.2 parts of nano-dispersant, 0.1-3.2 parts of aqueous stabilizer, and 15-55 parts of deionized water.

4. The method for preparing the full coverage high-precision graphene composite nano-ceramic coating according to claim 3, characterized in that: The preparation method of the nano deposition liquid is as follows: graphene, carbon nanotubes, nano silicon dioxide, nano aluminum oxide and nano zirconium oxide are dispersed in deionized water, a silane coupling agent is added for modification, and then a magnetoelectric ion composite agent, an ion regulator, an ion crosslinking agent, a nano dispersant and an aqueous stabilizer are added, and the mixture is stirred evenly and then matured.

5. The method for preparing the full coverage high-precision graphene composite nano-ceramic coating according to claim 4, characterized in that: The magnetic ion complex comprises one or more of [bmim]FeCl4, [bpy]FeCl4, [bmp]FeCl4 and [pbmim](FeCl4)2.

6. The method for preparing the full coverage high-precision graphene composite nano-ceramic coating according to claim 2, 4 or 5, characterized in that: During the first liquid phase nano-deposition, the magnetic field force is 10-30N, and the deposition time is 0.1-1.0h; during the second liquid phase nano-deposition, the magnetic field force is 50-150N, and the deposition time is 0.1-1h; during the third liquid phase nano-deposition, the magnetic field force is 200-400N, and the deposition time is 0.1-1h.

7. The method for preparing the full coverage high-precision graphene composite nano-ceramic coating according to claim 6, characterized in that: During the impurity removal treatment, the magnetic field force is 100-500N and the time is 6-60min.

8. The method for preparing the full coverage high-precision graphene composite nano-ceramic coating according to claim 7, characterized in that: The magnetic field force during the gas phase nano deposition is 100-500N and the time is 0.5-8h.

Images