CN110484866B - Preparation method of aluminum alloy surface anticorrosive coating - Google Patents

Preparation method of aluminum alloy surface anticorrosive coating Download PDF

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CN110484866B
CN110484866B CN201910835045.3A CN201910835045A CN110484866B CN 110484866 B CN110484866 B CN 110484866B CN 201910835045 A CN201910835045 A CN 201910835045A CN 110484866 B CN110484866 B CN 110484866B
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aluminum alloy
quartz tube
putting
intermetallic compound
coating
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CN110484866A (en
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苏旭平
须烨楠
刘亚
王建华
吴长军
涂浩
彭浩平
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5853—Oxidation

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a preparation method of an aluminum alloy surface anticorrosive coating, which is characterized by comprising the following steps: heating a container filled with Mg blocks and aluminum alloy at 520 +/-5 ℃ in a vacuum environment, evaporating the Mg blocks to form Mg vapor, evaporating the Mg vapor to the surface of the aluminum alloy to form an intermetallic compound, and oxidizing the aluminum alloy to generate a Mg-Al-O oxide coating to cover the Mg-Al intermetallic compound layer. The method has the advantages that the method does not need to carry out complicated operation, has lower cost and short time consumption, and the oxidation treatment coating after evaporation can be finished only by putting the aluminum alloy into a box-type furnace.

Description

Preparation method of aluminum alloy surface anticorrosive coating
Technical Field
The invention belongs to the technical field of surface coating preparation, and particularly relates to a preparation method of an aluminum alloy surface anticorrosive coating, in particular to a Mg-Al-O oxide double composite coating which is prepared by evaporating Mg on an aluminum alloy surface to generate a Mg-Al compound and then oxidizing the Mg-Al compound.
Background
The aluminum and the aluminum alloy have the advantages of high strength, low density, strong electric and thermal conductivity, excellent mechanical property, good machinability and the like, and are widely applied to the fields of chemical industry, aerospace industry, automobile manufacturing industry, food industry, electronic instrument industry, marine ship industry and the like. Aluminum and its alloys tend to form an oxide film with a thickness of about 4nm with oxygen in the air, but this oxide film is not dense, non-uniform and has poor corrosion resistance, and cannot resist corrosion in a severe environment. In addition, aluminum and its alloys are also susceptible to electrochemical corrosion with seawater, reducing their useful life. In order to solve the above problems, the surface of the aluminum alloy needs to be protected, and preparing one or more layers of corrosion-resistant coatings on the surface of the aluminum alloy is an ideal solution.
At present, the preparation of the metal thin film generally adopts Physical Vapor Deposition (PVD) technology. PVD (physical vapor deposition) technology, which was widely used for the preparation of excellent protective films, appeared in the 70's of the 20 th century. It is suitable for various base materials and various coating materials. Compared with CVD (chemical vapor deposition) process, the PVD process has low treatment temperature and has no influence on the bending strength of the base material below 600 ℃; the internal stress state of the plating layer is compressive stress, so that the method is more suitable for coating treatment of hard alloy materials; the PVD process has no adverse effect on the environment, conforms to the development direction of the line-generation green manufacturing, and is a typical pollution-free and zero-emission technology. With the more and more outstanding contradiction between modern industrial development and environmental protection, people put forward high requirements on the quality and service life of products, and the PVD surface engineering technology is just produced under the technical background. The PVD technique is one of the main techniques of the surface processing treatment at present and in the future due to the characteristics of incomparable traditional surface treatment, namely ultrathin, high temperature resistance and no pollution. The invention is different from the traditional vacuum evaporation, the vacuum evaporation machine is not needed for evaporation when the evaporation is carried out, but the substrate material and the evaporation material are sealed in the same quartz tube, and the quartz tube is placed in a box-type furnace for evaporation, thereby greatly reducing the cost. The single intermetallic compound film has limited protection on the substrate material, the evaporated substrate material is oxidized, the selective oxidation promotes the alloy elements to be enriched to the surface to form an oxidation film with complete compactness and strong compactness, and the high-temperature oxidation resistance or corrosion resistance of the metal material can be improved by pre-oxidizing the surface modification under the low oxygen pressure condition. The invention aims to prepare a layer of oxide film to cover the evaporation coating and carry out double protection on a substrate.
Disclosure of Invention
The invention aims to provide a novel method for preparing a Mg-Al intermetallic compound and Mg-Al-O oxide double composite coating. The composite coating is prepared by fewer processes and time, so that resources are saved, and the material design is more flexible.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of an aluminum alloy surface anticorrosive coating comprises the following steps: heating a container filled with Mg blocks and aluminum alloy at 520 +/-5 ℃ in a vacuum environment, evaporating the Mg blocks to form Mg vapor, evaporating the Mg vapor to the surface of the aluminum alloy to form an intermetallic compound, and oxidizing the aluminum alloy to generate a Mg-Al-O oxide coating to cover the Mg-Al intermetallic compound layer.
Further, the method comprises the following specific steps:
(1) processing the aluminum alloy into sheets, performing surface pretreatment on the sheets, and performing ultrasonic cleaning by using alcohol and acetone;
(2) putting the aluminum alloy treated in the step (1) into a quartz tube, then burning and sinking the middle part of the quartz tube to divide the quartz tube into two mutually communicated containing cavities, then putting a weighed Mg block to divide the Mg block and the aluminum alloy into the two containing cavities, and then sealing and vacuumizing;
(3) setting the temperature of a box furnace to 520 +/-5 ℃, putting the quartz tube sealed in the step (2) into the box furnace, ensuring that a magnesium block is arranged above and an aluminum alloy is arranged below, and evaporating for 5-10h to obtain an Mg-Al intermetallic compound layer formed on the surface of the aluminum alloy;
(4) and (4) putting the aluminum alloy subjected to vapor deposition in the step (3) into a box furnace at the temperature of 300 +/-10 ℃, preserving the heat for 0.5h +/-10 min, and taking out the aluminum alloy to obtain the Mg-Al-O oxide coating, wherein the Mg-Al-O oxide coating covers the Mg-Al intermetallic compound layer.
The method has the advantages that the method does not need to carry out complicated operation, has lower cost and short time consumption, and the oxidation treatment coating after evaporation can be finished only by putting the aluminum alloy into a box-type furnace.
Drawings
FIG. 1 is a schematic view of a quartz tube after vacuum sealing in examples 1 to 3, wherein: 1. magnesium block, 2 recess, 3 quartz tube, 4 aluminum block
FIG. 2 is a scanning electron microscope image of the surface and cross section of the aluminum alloy of example 1 after vapor deposition at 520 ℃ for 5 hours, wherein (a) is the surface and (b) is the cross section.
FIG. 3 is a scanning electron microscope image of the surface and cross section of the aluminum alloy of example 2 after vapor deposition at 520 ℃ for 10 hours, wherein (a) is the surface and (b) is the cross section.
FIG. 4 is a scanning electron micrograph showing the surface and cross section of an aluminum alloy in comparative example 1 after deposition at 520 ℃ for 15 hours, wherein (a) is the surface and (b) is the cross section.
Fig. 5 shows the oxidized surfaces of the samples after vapor deposition in example 2 and comparative example 1, where (a) vapor deposition was performed for 10 hours and (b) vapor deposition was performed for 15 hours.
Fig. 6 is a comparison of the uniformity of the Mg-Al intermetallic compound layer on the surface of the aluminum alloy after evaporation in example 1 and comparative example 2, wherein fig. 6(a) is a characterization of the uniformity of the Mg-Al intermetallic compound layer on the surface of the aluminum alloy after evaporation in example 1 and fig. 6(b) is a characterization of the uniformity of the Mg-Al intermetallic compound layer on the surface of the aluminum alloy after evaporation in comparative example 2.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1:
a preparation method of an aluminum alloy surface anticorrosive coating comprises the following steps:
(1) cutting the aluminum alloy into Al sheets of 1cm × 1cm × 0.5cm size by wire cutting;
(2) grinding and polishing the cut aluminum alloy by using No. 600 and No. 1000 SiC abrasive paper respectively, removing oil stains on the surface by using an alkaline degreasing agent, and then using 85% of H3PO4Etching for 30-40 s, removing a surface oxide film, cleaning with distilled water, soaking in absolute ethyl alcohol for later use, and weighing 2g of Mg blocks;
(3) placing the treated Al sheet into a quartz tube, vacuumizing to burn and recess the middle part of the quartz tube and divide the quartz tube into two mutually communicated containing cavities, cooling the quartz tube, then placing a weighed Mg block into the quartz tube to separate the Mg block and the Al sheet into the two containing cavities (namely the middle part of the quartz tube is not closed, so that the Al sheet and the Mg block are separated and Mg steam can flow at the same time, see figure 1), and sealingVacuum degree (vacuum degree less than 1 × 10)-3MPa)。
(4) And (2) putting the sealed quartz tube into a box furnace, ensuring that the magnesium block is on the top and the aluminum alloy is on the bottom, setting the temperature at 520 ℃ and evaporating for 5 hours to form a Mg-Al intermetallic compound layer with the thickness of about 1.5um on the surface of the Al sheet, wherein as shown in figure 2, the coating is not uniformly distributed on the surface of the aluminum alloy, and the evaporated Mg is mainly distributed on the surface of the aluminum alloy in a strip shape. It is shown that under the experimental conditions, the magnesium element can not be completely evaporated, and the surface of the substrate is not greatly changed.
Example 2:
a preparation method of an aluminum alloy surface anticorrosive coating comprises the following steps:
(1) cutting the aluminum alloy into Al sheets of 1cm × 1cm × 0.5cm size by wire cutting;
(2) grinding and polishing the cut aluminum alloy by using No. 600 and No. 1000 SiC abrasive paper respectively, removing oil stains on the surface by using an alkaline degreasing agent, and then using 85% of H3PO4Etching for 30-40 s, removing a surface oxide film, cleaning with distilled water, soaking in absolute ethyl alcohol for later use, and weighing 2g of Mg blocks;
(3) placing the treated Al sheet into a quartz tube, vacuumizing to burn and recess the middle part of the quartz tube and divide the quartz tube into two mutually communicated containing cavities, cooling the quartz tube, then placing an Mg block into the quartz tube to separate the Mg block and the Al sheet into the two containing cavities (the middle part of the quartz tube is not closed, so that the Al sheet and the Mg block can be separated and Mg steam can flow at the same time, see figure 1), sealing and vacuumizing (the vacuum degree is less than 1 x 10)-3MPa)。
(4) And (3) putting the sealed quartz tube into a box-type furnace, ensuring that a magnesium block is on the top and an aluminum alloy is on the bottom, setting the temperature at 520 ℃ and evaporating for 10 hours to form a Mg-Al intermetallic compound layer with the thickness of about 3um on the surface of the Al sheet, wherein as shown in figure 3, a more uniform coating is formed on the surface of the aluminum alloy, but the coating is not flat, the coverage rate of the coating is greatly improved compared with that of figure 2, and the thickness of the coating is also improved compared with that of figure 2.
(5) And (3) taking out the evaporated Al sheet, putting the Al sheet into a box furnace, setting the temperature to be 300 ℃, and preserving the heat for 0.5h to regenerate a layer of Mg-Al-O oxide film on the original coating, wherein as shown in figure 5(a), the surface of the oxidized coating becomes smoother and more compact.
Comparative example 1:
a preparation method of an aluminum alloy surface anticorrosive coating comprises the following steps:
(1) cutting the aluminum alloy into Al sheets of 1cm × 1cm × 0.5cm size by wire cutting;
(2) grinding and polishing the cut aluminum alloy by using No. 600 and No. 1000 SiC abrasive paper respectively, removing oil stains on the surface by using an alkaline degreasing agent, and then using 85% of H3PO4Etching for 30-40 s, removing a surface oxide film, cleaning with distilled water, soaking in absolute ethyl alcohol for later use, and weighing 2g of Mg blocks;
(3) placing the treated Al sheet into a quartz tube, vacuumizing to burn and recess the middle part of the quartz tube and divide the quartz tube into two mutually communicated containing cavities, cooling the quartz tube, then placing an Mg block into the quartz tube to separate the Mg block and the Al sheet into the two containing cavities (namely the middle part of the quartz tube is not closed, so that the Al sheet and the Mg block can be separated and Mg steam can flow at the same time, see figure 1), sealing and vacuumizing (the vacuum degree is less than 1 x 10)-3MPa)；
(4) And (3) putting the sealed quartz tube into a box furnace, ensuring that the magnesium block is on the top and the aluminum alloy is on the bottom, setting the temperature to 520 ℃, and evaporating for 15 hours to form an Mg-Al intermetallic compound layer with the thickness of about 2um on the surface, wherein as shown in figure 4, compared with figure 3(a), the compactness of the coating is reduced to a certain extent, and the unevenness is also improved compared with figure 3 (a).
(5) And (3) taking out the evaporated Al sheet, putting the Al sheet into a box furnace, setting the temperature to be 300 ℃, and preserving the heat for 0.5h to regenerate a layer of Mg-Al-O oxide film on the original coating, wherein the surface of the oxidized coating becomes smoother and more compact as shown in figure 5 (b).
Comparative example 2:
based on the embodiment 1, the other steps are the same as the embodiment 1 except that in the step (4), the sealed quartz tube is placed into a box type furnace, and the magnesium block is arranged below and the aluminum alloy is arranged above. As shown in FIG. 6(b), the uniformity and the density of the Mg-Al intermetallic compound layer obtained after the vapor deposition were inferior to those of the Mg-Al intermetallic compound layer obtained in example 1.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.

Claims (2)

1. A preparation method of an aluminum alloy surface anticorrosive coating is characterized by comprising the following steps: heating a container filled with Mg blocks and aluminum alloy at 520 +/-5 ℃ in a vacuum environment, evaporating the Mg blocks to form Mg vapor, evaporating the Mg vapor to the surface of the aluminum alloy to form an intermetallic compound, and oxidizing the aluminum alloy to generate a Mg-Al-O oxide coating to cover the Mg-Al intermetallic compound layer, wherein the oxidation temperature is 300 +/-10 ℃.
2. The preparation method of the aluminum alloy surface anticorrosive coating according to claim 1, characterized by comprising the following steps:
(1) processing aluminum alloy into an aluminum sheet, performing surface pretreatment on the aluminum sheet, and performing ultrasonic cleaning by using alcohol and acetone;
(2) putting the aluminum alloy treated in the step (1) into a quartz tube, then burning and sinking the middle part of the quartz tube to divide the quartz tube into two mutually communicated containing cavities, then putting a weighed Mg block, putting the Mg block and the aluminum alloy into the containing cavities respectively, and then sealing and vacuumizing;
(3) setting the temperature of a box furnace to 520 +/-5 ℃, putting the quartz tube sealed in the step (2) into the box furnace, ensuring that a magnesium block is arranged above and an aluminum alloy is arranged below, and evaporating for 5-10h to obtain an Mg-Al intermetallic compound layer formed on the surface of the aluminum alloy;
(4) and (4) putting the aluminum alloy subjected to vapor deposition in the step (3) into a box furnace at the temperature of 300 +/-10 ℃, preserving the heat for 0.5h +/-10 min, and taking out the aluminum alloy to obtain the Mg-Al-O oxide coating, wherein the Mg-Al-O oxide coating covers the Mg-Al intermetallic compound layer.
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CN112111708B (en) * 2020-09-18 2023-05-23 常州大学 Method for improving corrosion resistance of surface of high-alumina brick refractory material in zinc pot
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Citations (2)

* Cited by examiner, † Cited by third party
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CN1315988A (en) * 1998-08-31 2001-10-03 西柏控股有限公司 Optically variable pigments providing colour shift between two distinct colours, coating composition comprising the same, method for producing the same
EP2752504A1 (en) * 2013-01-08 2014-07-09 ROPAL Europe AG Method for producing a corrosion resistant, glossy, metallic coated substrate, the metallic coated substrate, and its use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1315988A (en) * 1998-08-31 2001-10-03 西柏控股有限公司 Optically variable pigments providing colour shift between two distinct colours, coating composition comprising the same, method for producing the same
EP2752504A1 (en) * 2013-01-08 2014-07-09 ROPAL Europe AG Method for producing a corrosion resistant, glossy, metallic coated substrate, the metallic coated substrate, and its use

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