阅读说明：本技术 一种智能车库防腐蚀膜层及其制备方法 (Intelligent garage anti-corrosion film layer and preparation method thereof ) 是由 黄超 王春雷 陈长明 阎娟 黄仲佳 吴路路 孙宇峰 王刚 于 2020-06-11 设计创作，主要内容包括：本发明所述的一种智能车库防腐蚀膜层,包括至少一层氮化物保护膜层,所述氮化物保护膜层均包括碳化钒组成的底层、氮化钒铝混合化合物组成的中间层和膨化铬组成的第三层,以及制备上述防腐蚀膜层的方法。本发明所述的有益效果为：多层结构材质为VN/VAlN/CrB,属于金属化合物类,与有机类涂料相比其热膨胀系数与金属接近,性能更为稳定,防腐性能更好。(The invention relates to an intelligent garage anti-corrosion film layer which comprises at least one nitride protection film layer, wherein the nitride protection film layer comprises a bottom layer composed of vanadium carbide, a middle layer composed of a vanadium-aluminum nitride mixed compound and a third layer composed of expanded chromium, and a method for preparing the anti-corrosion film layer. The invention has the beneficial effects that: the multilayer structure material is VN/VAlN/CrB, belongs to metal compounds, and compared with organic coatings, the thermal expansion coefficient of the multilayer structure material is close to that of metal, the performance is more stable, and the corrosion resistance is better.)

1. The anti-corrosion film layer for the intelligent garage is characterized by comprising at least one nitride protection film layer, wherein the nitride protection film layer comprises a bottom layer composed of vanadium carbide, a middle layer composed of a vanadium aluminum nitride mixed compound and a third layer composed of expanded chromium.

2. The preparation method of the anti-corrosion film layer for the intelligent garage according to claim 1, comprising the steps of,

s1: adopting multi-arc vacuum evaporation deposition equipment, respectively installing 1 aluminum target, 1 vanadium target and one chromium boride target on 3 targets of the multi-arc vacuum evaporation deposition equipment, and etching and cleaning the 3 heavy targets;

s2: starting the working state of the vanadium target, filling nitrogen into the equipment, and depositing to obtain a vanadium carbide transition layer;

s3: simultaneously starting the working states of the vanadium target and the aluminum target, introducing high-purity nitrogen flow, and depositing to obtain a vanadium-aluminum nitride mixed compound layer;

s4: and closing the working states of the vanadium target and the aluminum target, opening the working state of the chromium boride target, and depositing to obtain the expanded chromium layer.

3. The method for preparing an anticorrosion film layer for an intelligent garage, according to claim 2, is characterized in that the steps of S2, S3 and S4 are repeated to alternately deposit a vanadium carbide layer, a vanadium aluminum nitride compound layer and a puffed chromium layer in no less than 3 layers, and the last layer is a puffed chromium layer.

4. The preparation method of the intelligent garage anti-corrosion film layer according to any one of claims 2 or 3, wherein the aluminum target, the vanadium target and the chromium boride target are respectively etched and cleaned for 2min under negative bias of-900V, -1100V and-1200V, and surface oxide films and impurities are eliminated.

5. The method for preparing an intelligent garage anti-corrosion film layer according to any one of claims 2 or 3, wherein in S2, when a vanadium target working state is started, the process conditions are set to be a current of 60A-75A, a bias voltage of-50V-55V, and a deposition time of 6-8 min.

6. The method for preparing an intelligent garage anti-corrosion film layer according to any one of claims 2 or 3, wherein in S3, when the vanadium target and the aluminum target are simultaneously turned on, the current is 60A-75A and 30-45A respectively, the flow rate of high-purity nitrogen gas is 350sccm, and the deposition time is 5-7 min.

7. The method for preparing an intelligent garage anti-corrosion film layer according to any one of claims 2 or 3, wherein in S4, when the working state of the vanadium target and the aluminum target is closed and the working state of the chromium boride target is opened, the process conditions are set to be 40A-55A of current, the bias voltage is-50V-55V, and the deposition time is 8-10 min.

Technical Field

The invention relates to the field of corrosion prevention of intelligent parking garages, in particular to an intelligent garage corrosion prevention film layer and a preparation process thereof.

Background

The intelligent garage is generally arranged in a basement or outdoors and can generate rust when being eroded by humid air, particularly the intelligent garage in coastal areas, the intelligent garage receives the corrosion of seawater and moisture and has a great influence on the service life, or the intelligent garage can pollute and stop vehicles when rusty water occurs in rainy days.

At present, the steel structure part of the garage is mostly constructed by adopting fireproof paint, the bottom coat of the fireproof paint of the garage is sprayed by adopting gravity or a spray gun, and the garage is roughly divided into a thin protective coat and a thick protective coat.

The thickness of the thin coating is generally 2 mm-7 mm, the pressure of the thin coating is about 0.4MPa, the bottom layer is generally sprayed for 2-3 times, the thickness of each time is not more than 2.5mm, the surface layer decorative coating can be brushed, sprayed or rolled after the previous drying, the surface layer decorative coating can be brushed, sprayed or rolled after the spraying, the surface layer is generally painted for 1-2 times, the color of the surface layer is uniform, the stubbles are smooth, the final leveling treatment is carried out, the uniformity and smoothness are ensured, an operator needs to carry a thickness tester to detect the thickness of the coating, and the spraying is ensured to reach the designed thickness.

The thickness of the thick coating is generally 8 mm-15 mm, the thick coating is in a powdery surface, the density is small, the thermal conductivity is low, and the fire resistance limit can reach 2.5 h-5.0 h. The thick fireproof paint is sprayed by a pressure-feed spraying machine, the air pressure is カ 0.4-0.4 MPa, the diameter of a spray gun opening is 6-10 mm, and the thick fireproof paint is added or diluted by a proper proportion strictly during proportioning and is matched with the thick fireproof paint while the thick fireproof paint is mixed. The spraying construction should survive by several times, the spraying thickness of each time is preferably 5 mm-7 mm, and the spraying must be carried out after the primary drying and curing. In the spraying process, an operator needs to adopt a thickness measuring needle to detect the thickness of the sensing coating until the thickness reaches the thickness specified by the design, and the spraying can be stopped.

In conclusion, the garage anticorrosive coating is required to have fireproof performance and anticorrosive performance, and the fireproof coating in the current market can basically meet the requirements, but the following defects still exist: (1) the coating has aging property, the service life of the coating (usually 20 years) is often far shorter than that of a garage (usually the service life is designed to be more than 40 years), and the coating needs to be repaired regularly; (2) as the fireproof coating is organic matter and the garage structural part is metal, the expansion coefficient difference between the fireproof coating and the garage structural part is too much, and the paint coating can locally bubble under the conditions of high temperature and sunlight within the whole service life of 20 years of the coating, so that the coating layer is damaged, the garage generates rusty spots, rusty water of an outdoor parking garage pollutes and parks vehicles in rainy days, and the mechanical property of a local corrosion position of a serious person is reduced, so that safety accidents are caused.

Disclosure of Invention

In order to solve the technical problem, the invention provides an intelligent garage anti-corrosion film layer which comprises at least one nitride protection film layer, wherein the nitride protection film layer comprises a bottom layer composed of vanadium carbide (VN), a middle layer composed of vanadium aluminum nitride (VAIN) and a third layer composed of expanded chromium (CrB).

The preparation method of the anti-corrosion film layer of the intelligent garage comprises the following steps,

s1: adopting multi-arc vacuum evaporation deposition equipment, respectively installing 1 aluminum target, 1 vanadium target and a chromium boride target on 3 targets, respectively etching and cleaning the 3 heavy targets under negative bias of-900V, -1100V and-1200V for 2min, and eliminating surface oxide films and impurities;

s2: starting a vanadium target (99.95 at.%) in a working state, setting the current to be 60-75A, and filling nitrogen into the equipment under the process conditions that the bias voltage is-50V-55V, and the deposition time is 6-8min to obtain a vanadium carbide (VN) transition layer;

s3: simultaneously starting the working states of a vanadium target and an aluminum target, wherein the current is 60A-75A and 30-45A respectively, high-purity nitrogen (99.99%) is introduced, the flow rate is 350sccm, and a vanadium-aluminum nitride mixed compound (VAIN) layer is obtained after deposition for 5-7 min;

s4: and closing the working state of the vanadium target and the aluminum target, starting the working state of the chromium boride target, setting the current to be 40-55A, and depositing for 8-10min under the process condition that the bias voltage is-50V-55V to obtain the expanded chromium (CrB) layer.

Further, 3 or more layers of vanadium carbide (VN) layer, vanadium aluminum nitride (VAIN) layer and expanded chromium (CrB) layer can be deposited alternately in a circulating mode by selecting circulating and alternating S2, S3 and S4 to prepare the nano multilayer structure coating, and the final layer is the expanded chromium (CrB) layer to prevent the surface from obtaining a cover surface layer with high wear-resistant corrosion performance.

The preparation method adopts the technical scheme that:

the invention has the beneficial effects that: (1) the multilayer structure material of the invention is VN/VAlN/CrB, belongs to metal compounds, and has a thermal expansion coefficient close to that of metal compared with organic coatings. The performance is more stable; (2) vanadium, aluminum and chromium metal elements are adopted to react in the deposition process to form VN, VAlN and CrB metal compounds with inert characteristics, and the corrosion resistance is realized.

Drawings

In order that the present invention may be more readily and clearly understood, there now follows a more particular description of the invention in terms of specific embodiments and reference to the accompanying drawings.

Fig. 1 shows an anti-corrosion film layer of a multilayer structure according to the present invention.

Fig. 2 shows the corrosion-resistant film layer of the multilayer structure after 720 hours of salt spray corrosion.

FIG. 3 is a spectrum scan of the coating after 720 hours salt spray corrosion.

Detailed Description

The invention relates to an intelligent garage anti-corrosion film layer which comprises at least one nitride protection film layer, wherein the nitride protection film layer comprises a bottom layer composed of vanadium carbide (VN), a middle layer composed of vanadium aluminum nitride (VAIN) mixed compound and a third layer composed of expanded chromium (CrB).

The preparation method of the anti-corrosion film layer of the intelligent garage comprises the following steps,

s1: adopting multi-arc vacuum evaporation deposition equipment, respectively installing 1 aluminum target, 1 vanadium target and a chromium boride target on 3 targets, respectively etching and cleaning the 3 heavy targets under negative bias of-900V, -1100V and-1200V for 2min, and eliminating surface oxide films and impurities;

the 3 target positions can be respectively provided with different materials in the 3 target positions, and the preparation of a multilayer structure is facilitated. The 3 target position negative bias voltages are respectively corresponding to the removal voltage positions of the oxide film and the impurities on the surface of the three targets.

S2: starting a vanadium target (99.95 at.%) in a working state, setting the current to be 60A, and filling nitrogen into the equipment under the process condition that the bias voltage is-50V, wherein the deposition time is 6min to obtain a vanadium carbide (VN) transition layer;

s3: simultaneously starting the working states of a vanadium target and an aluminum target, wherein the current is respectively 60A and 30A, high-purity nitrogen (99.99%) is introduced, the flow rate is 350sccm, and a vanadium-aluminum nitride mixed compound (VAIN) layer is obtained after deposition for 5 min; s4: and closing the working states of the vanadium target and the aluminum target, opening the working state of the chromium boride target, setting the current to be 40A, and depositing for 8min under the process condition that the bias voltage is-50V to obtain the expanded chromium (CrB) layer.

S5: optionally repeating S2, S3 and S4, and alternately depositing a vanadium carbide (VN) layer, a vanadium aluminum nitride (VAIN) layer and a puffed chromium (CrB) layer in a circulating way to form a composite film with 3 layers or a film with 6 or more layers to prepare the nano multilayer structure coating, wherein the final layer is the puffed chromium (CrB) layer to prevent the surface from obtaining a cover surface layer with high wear-resistant corrosion resistance.

The multilayer structure coating is shown in fig. 1, and the total coating thickness h is 2.257 micrometers.

The first layer deposited VN is because the coating has high bonding strength with an iron matrix, plays a role of a transition layer and has good corrosion resistance; CrB is adopted for surface covering because of high inertia, good corrosion resistance and thermal stability. The alternate preparation of 3 coatings, the interface between the coatings is favorable to further hinder the corrosive attack.

And (3) placing the coating in a smoke tester, and carrying out salt spray corrosion performance tests in different test times by adopting an artificial seawater corrosive liquid to evaluate the corrosion resistance of the coating. The corrosion time is 240h, 480h and 720h respectively, and the coating still maintains a relatively complete structure after the smoke corrosion of 720h, only the multi-layer structure of the coating becomes fuzzy (see figure 2), so that the multi-layer coating disclosed by the invention shows good stability in a marine corrosion environment.

The cross-section element distribution map analysis is carried out on the corrosion coating, and the fact that the 720-hour salt spray corrosion does not cause chloride ions to diffuse into the coating is found, which shows that the multilayer coating has better corrosion resistance to the chloride ions in the marine corrosion environment.

The comparison table of the performances of the VN/VAlN/CrB multilayer structure anticorrosive coating and the commercially available steel structure fireproof coating layer is shown in Table 1, and the beneficial effects obtained by the invention are as follows: (1) the multilayer structure material is VN/VAlN/CrB, belongs to metal compounds, and has a thermal expansion coefficient close to that of metal compared with organic coatings. In the salt spray experiment, the salt spray solution with 100 ℃ is continuously sprayed for 720 hours, and phenomena such as foaming and falling-off do not occur. (2) Vanadium, aluminum and chromium metal elements are adopted to react in the deposition process to form VN, VAlN and CrB metal compounds with inert characteristics, and the compounds have corrosion resistance (rust spots, bubbles and the like do not appear in 720h of a salt spray experiment), and the service life of the compounds is longer than 40 years according to the evaluation of salt work experiment data.

Table 1 VN/VAlN/CrB multilayer structure anticorrosion and paint coating performance comparison table:

and (3) analyzing the reason of local discoloration in a VN/VAlN/CrB multilayer structure in a 720-hour salt spray experiment, scanning the corroded coating in the direction from the substrate to the surface of the coating by adopting energy spectrum analysis, and scanning energy spectrums at 3 positions in total, wherein the figure is shown in figure 3. The result shows that the coating is not penetrated by chloride ions, and elements of the coating are distributed as shown in figure 3, so that the discoloration of the surface is caused by the fact that the iron matrix is corroded and polluted on the surface of the coating by the solution, and the anti-corrosion film layer prepared by the preparation method is stable and has longer service life.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention further, and all equivalent variations made by using the contents of the present specification and the drawings are within the protection scope of the present invention.