CN108300844B - Anti-corrosion sandwich structure and construction method thereof - Google Patents
Anti-corrosion sandwich structure and construction method thereof Download PDFInfo
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- CN108300844B CN108300844B CN201810070331.0A CN201810070331A CN108300844B CN 108300844 B CN108300844 B CN 108300844B CN 201810070331 A CN201810070331 A CN 201810070331A CN 108300844 B CN108300844 B CN 108300844B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/06—Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/08—Modifying the physical properties of iron or steel by deformation by cold working of the surface by burnishing or the like
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/03—Amorphous or microcrystalline structure
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Abstract
The invention relates to the field of coatings, in particular to an anticorrosive sandwich structure and a construction method thereof. The anticorrosion sandwich structure comprises an alloy matrix, an alloy surface layer and a coating; the content of at least one element in the alloy surface layer is different from that of the element in the alloy matrix; the alloy surface layer is provided with a nanocrystalline structure and/or an ultrafine grain structure; the thickness of the alloy surface layer is more than or equal to 50 microns. The preparation method comprises the following steps: taking an alloy matrix; carrying out surface severe plastic deformation on the alloy matrix; forming a plastic deformation layer with the thickness of more than 50 microns on the surface layer of the alloy; then carrying out heat treatment to obtain a surface segregation layer of the alloy elements; then coating a layer of anticorrosive paint on the surface of the alloy; obtaining an antiseptic sandwich structure; the temperature of the heat treatment is less than or equal to the highest stable existing temperature of the nanocrystalline structure and/or the ultrafine-grained structure in the alloy surface layer. The invention has simple process and is convenient for large-scale industrial application.
Description
Technical Field
The invention relates to the field of coatings, in particular to an anticorrosive sandwich structure and a construction method thereof.
Background
The coating is widely applied to the field of metal corrosion protection. However, metals are often exposed to aggressive environments due to local defects or external scratches of the coating, etc. In many cases, such as when the metal to be protected by the coating is joined to a more inert metal part, localized coating failure results in a significant increase in the cathode/anode area ratio, resulting in severe depth-to-depth metal corrosion at the failure site. The local corrosion developed in the depth direction is hidden and dangerous, which often causes production accidents. The reduction of the risk of safety accidents caused by local failure of the coating has great engineering and technical significance.
Disclosure of Invention
In view of the above-mentioned deficiencies and drawbacks of the prior art, it is an object of the present invention to provide an antiseptic "sandwich" structure and method of construction thereof.
It is another object of the present invention to alter the direction of localized corrosion development after coating failure.
Another object of the invention is to reduce the production risk caused by localized corrosion of coating failures.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the invention relates to an anticorrosion sandwich structure, which comprises an alloy matrix, an alloy surface layer and a coating; the content of at least one element in the alloy surface layer is different from that of the element in the alloy matrix; the alloy surface layer is provided with a nanocrystalline structure and/or an ultrafine grain structure; the thickness of the alloy surface layer is more than or equal to 50 microns. Preferably, the thickness of the alloy surface layer is 50-500 microns.
The preferred range of the grain size of the nanocrystals in the present invention is 5nm to 100 nm.
As a preferred scheme, the anticorrosion sandwich structure comprises an alloy matrix, an alloy surface layer and a coating; the alloy surface layer and the alloy matrix are consistent in component element type; but the content of at least one element in the alloy surface layer is different from that of the element in the alloy matrix; the alloy surface layer is provided with a nanocrystalline structure and/or an ultrafine grain structure; the thickness of the alloy surface layer is more than or equal to 50 microns. Preferably, the thickness of the alloy surface layer is 50-500 microns. There is no obvious interface between the alloy surface layer and the alloy matrix.
The invention relates to an anticorrosion sandwich structure, and the coating comprises all anticorrosion coatings.
The invention relates to a construction method of an anticorrosion sandwich structure; the scheme is as follows: taking an alloy matrix; carrying out severe plastic deformation on the alloy matrix; forming a plastic deformation layer with the thickness of more than 50 microns on the surface layer of the alloy to obtain a sample with severe plastic deformation on the surface; carrying out heat treatment on the sample with the surface severely plastically deformed to obtain an alloy element surface layer segregation sample (in the alloy element surface layer segregation sample, the thickness of an element segregation layer is more than 5 micrometers); then coating a layer of anticorrosive paint on the surface of the coating; obtaining an antiseptic sandwich structure; the alloy surface layer is provided with a nanocrystalline structure and/or an ultrafine grain structure; the temperature of the heat treatment is less than or equal to the highest stable existing temperature of the nanocrystalline structure and/or the ultrafine-grained structure in the alloy surface layer.
The invention relates to a construction method of an anticorrosion sandwich structure; the severe plastic deformation comprises at least one of shot blasting, ultrasonic shot blasting, sand blasting, laser shot blasting, high pressure water shot blasting, surface mechanical grinding, surface mechanical milling and surface mechanical rolling. In the present invention, the thickness of the alloy surface layer having a nanocrystalline structure and/or ultrafine-grained structure is generally controlled by the time and speed of shot blasting. Preferably, the shot blasting has a shot diameter of 1 to 10mm, a shot blasting speed of generally 1 to 100m/s, and a time of 5 to 120 min. Preferably, the shot diameter is 3 to 6mm, the shot blasting speed is generally 5 to 15m/s, and the time is 5 to 15 min.
The invention relates to a construction method of an anticorrosion sandwich structure; after severe plastic deformation and heat treatment, the open circuit potential of the alloy surface layer is more negative than that of the alloy matrix.
The invention relates to a construction method of an anticorrosion sandwich structure; the alloy matrix includes, but is not limited to 7000 series aluminum alloys, austenitic stainless steels, brass, bronze.
The invention relates to a construction method of an anticorrosion sandwich structure;
when the alloy matrix is 7000 series aluminum alloy, the heat treatment temperature is room temperature-240 ℃;
when the alloy matrix is austenitic stainless steel, the heat treatment temperature is room temperature to 480 ℃;
when the alloy matrix is brass, the heat treatment temperature is room temperature to 550 ℃;
when the alloy matrix is bronze, the heat treatment temperature is room temperature-550 ℃.
As a preferred scheme, the invention relates to a construction method of an antiseptic sandwich structure; when the temperature for heat treatment is room temperature, the time for heat treatment is 1 week to 24 months. Namely natural aging for 1 week to 24 months.
In industrial applications, when the temperature of the heat treatment is higher than room temperature; the time for using the method can be shortened to 15min or even shorter; the heat treatment is favorable for enhancing the bonding strength of the coating. And after the coating is coated, the alloy surface layer is naturally aged when the workpiece is applied until the coating is damaged. This further facilitates the generation of lateral erosion.
Principles and advantages
The invention regulates and controls the structure and the components of the alloy surface layer through the violent plastic deformation of the surface with large energy and the subsequent heat treatment process, so that the alloy surface layer is a sacrificial anode relative to the alloy matrix. Then, in combination with the coating, the component alloy matrix-alloy skin-coating "sandwich" structural system.
In the invention, the purpose of the large-energy surface severe plastic deformation is to introduce a large amount of defects such as grain boundaries, dislocations and vacancies in the alloy surface layer, thereby greatly improving the solid solubility of the alloy elements in the alloy surface layer. The solid solubility of the alloy matrix element is unchanged, or the solid solubility of the subsurface element is increased to a limited extent, so that a solid solubility difference is formed between the alloy surface layer and the alloy matrix/subsurface layer, namely a chemical potential gradient is formed. The alloying elements tend to migrate from the subsurface/matrix to the surface of the alloy driven by the chemical potential gradient (i.e., lowering the gibbs free energy of the system). The purpose of the heat treatment is to form a surface segregation phenomenon, and alloy elements rapidly migrate from a subsurface layer to the surface layer along defects such as grain boundaries, dislocation pipelines and the like under the drive of reducing Gibbs free energy of a system, so that the alloy components of the surface layer and a matrix are obviously different. After heat treatment, the surface layer is a sacrificial anode layer relative to the substrate. After the coating is damaged, the anode layer can be corroded laterally; this is advantageous for protecting the alloy matrix. Meanwhile, when the anode layer with large area is damaged, the coating can fall off with large area; this facilitates viewing. Meanwhile, even if the coating is stripped in a large area, the corrosion of the alloy matrix is not serious at the moment, and early warning and sufficient time are provided for subsequent remediation.
Advantages of
1) The development direction of local corrosion after the coating fails is changed, and the development direction of the corrosion is changed from the longitudinal direction to the transverse direction.
2) And the safety factor of the engineering equipment is improved.
3) Due to the introduction of the nanocrystalline, the bonding force between the alloy and the coating is larger.
4) Compared with the method without introducing the coating, the corrosion rate of the alloy surface layer is obviously reduced, and the protection efficiency of the sacrificial anode layer is higher.
5) The method has wide application range and is suitable for all alloys of which the surface layer is a sacrificial anode layer relative to the matrix after severe plastic deformation and heat treatment.
Drawings
FIG. 1 is a schematic view of a sandwich structure;
FIG. 2 is a schematic view of severe plastic deformation of a surface (ultrasonic peening);
FIG. 3 is a change in the direction of corrosion development following a partial failure of the coating;
FIG. 4 is a cross-sectional metallographic view of 7034 aluminum alloy after ultrasonic peening treatment;
FIG. 5 shows segregation of the surface layer of the alloying elements of 7034 aluminum alloy after ultrasonic shot peening and heat treatment (× 1 years at room temperature);
FIG. 6 shows segregation of the surface layer of the alloying elements of 7034 aluminum alloy after ultrasonic shot peening and heat treatment (× deg.C for two months);
FIG. 7 is an open circuit potential of 7034 aluminum alloy after ultrasonic peening and heat treatment;
FIG. 8 is a microstructure, XRD, elemental segregation, and open circuit potential of SS304 stainless steel before and after ultrasonic peening treatment;
FIG. 9 is a microstructure, XRD and open circuit potential of C46400 brass before and after ultrasonic peening;
FIG. 10 is an elemental distribution plot of a cross-section of a C46400 copper alloy after ultrasonic peening.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The alloy used in this example was 7034 aluminum alloy. Sanding with 400 mesh sandpaper followed by ultrasonic peening experiments (fig. 2). The material of the shot blasting chamber is cast iron. The shot blasting adopted by the ultrasonic shot blasting test is stainless steel shots with the grain diameter of 4mm, the shot blasting distance is 11mm, the shot blasting speed is 8m/s, the ultrasonic amplitude is 56 micrometers, and the shot blasting time is 8 min.
The obtained alloy was characterized by metallographic microscopy, and the results are shown in fig. 4. It can be seen that the deformation depth is about 200 microns, and the surface structure has the phenomena of grain refinement and distortion. And (3) carrying out heat treatment on the 7034 aluminum alloy subjected to shot blasting treatment, wherein the heat treatment system is natural aging, and the natural aging time is 1 year. The element distribution of the resulting cross section is shown in fig. 5. It was found that the Zn content was greatly segregated in the surface layer, and the increase from 10 wt% before the pretreatment was 45 wt%. Similar elemental segregation results were obtained with heat treatment at 80 ℃ for 2 months, as shown in FIG. 6. As shown in fig. 7, the change in the distribution of elements causes the alloy open circuit potential to change, and the open circuit potential to shift negatively. After ultrasonic shot blasting and heat treatment, the 7034 aluminum alloy surface layer is a sacrificial anode layer relative to the matrix, a coating is coated, and the aluminum alloy surface layer is assembled into a sandwich structure shown in fig. 1, after the coating is locally failed, the local corrosion development direction of the alloy is transverse, namely the sacrificial anode layer is consumed firstly, and then the alloy can be deeply developed. The change of the corrosion development direction can obviously reduce the equipment failure risk caused by local corrosion of the coating.
Example 2
The alloy used in this example was 304 austenitic stainless steel. Sanding with 400 mesh sandpaper followed by ultrasonic peening experiments (fig. 2). The material of the shot blasting chamber is cast iron. The shot blasting adopted by the ultrasonic shot blasting test is stainless steel shots with the grain diameter of 4mm, the shot blasting distance is 11mm, the shot blasting speed is 10m/s, the ultrasonic amplitude is 56 micrometers, and the shot blasting time is 8 min.
The obtained alloy was characterized metallographically using a metalloscope, and the results are shown in fig. 8 a. It can be seen that the deformation depth is about 250 microns, and the superficial tissues show a high-density slip band. The XRD results (fig. 8b and 8c) show that martensitic transformation occurred in the 304 stainless steel surface layer after shot blasting. And (3) carrying out heat treatment on the 304 stainless steel subjected to shot blasting, wherein the heat treatment system is natural aging, and the heat treatment time is 1 year. The elemental distribution of the resulting cross-section is shown in fig. 8 d. As can be seen, the elemental content changes. Electrochemical measurements showed a negative shift in open circuit potential of the treated 304 stainless steel, as shown in fig. 8 e. This shows that after ultrasonic shot blasting and heat treatment, the 304 stainless steel surface layer is a sacrificial anode layer relative to the substrate, the coating is coated, and the structure is assembled into a sandwich structure shown in fig. 1, and after the coating is locally failed, the local corrosion development direction of the alloy is transverse, that is, the sacrificial anode layer is consumed first, so that the alloy can develop deeply. The change of the corrosion development direction can obviously reduce the equipment failure risk caused by local corrosion of the coating.
Example 3
The alloy used in this example was C46400 brass. Sanding with 400 mesh sandpaper followed by ultrasonic peening experiments (fig. 2). The material of the shot blasting chamber is cast iron. The shot blasting adopted by the ultrasonic shot blasting test is stainless steel shots with the grain diameter of 4mm, the shot blasting distance is 11mm, the shot blasting speed is 8m/s, the ultrasonic amplitude is 56 micrometers, and the shot blasting time is 8 min.
The obtained alloy is characterized by metallographic microscopy, the results are shown in figures 9 a-e, the deformation depth is about 250 microns, a high-density slip band appears on the surface layer tissue, XRD results (figure 9f) show that the preferred orientation of the brass surface layer is changed after shot blasting, the heat treatment is carried out on the C46400 brass after shot blasting, the heat treatment system is natural aging, and the heat treatment time is 1 year.
Comparative example 1
The other conditions were the same as in example 1 except that the coating was not shot-blasted, and was directly coated with an anticorrosive coating after being directly sanded with 400-mesh sandpaper. The corrosion of the resulting coating is shown in the left panel of fig. 3.
Claims (5)
1. An anticorrosive "sandwich" structure which characterized in that: the anticorrosion sandwich structure comprises an alloy matrix, an alloy surface layer and a coating; the content of at least one element in the alloy surface layer is different from that of the element in the alloy matrix; the alloy surface layer is provided with a nanocrystalline structure and/or an ultrafine grain structure; the thickness of the alloy surface layer is more than or equal to 50 micrometers; the alloy surface layer is a sacrificial anode layer relative to the substrate; the antiseptic "sandwich" structure is constructed by the following steps: taking an alloy matrix; carrying out severe plastic deformation on the alloy matrix; forming a plastic deformation layer with the thickness of more than 50 microns on the surface layer of the alloy to obtain a sample with severe plastic deformation on the surface; carrying out heat treatment on the sample with the surface subjected to severe plastic deformation to obtain an alloy element surface layer segregation sample; then coating a layer of anticorrosive paint on the surface of the coating; obtaining an antiseptic sandwich structure; the alloy surface layer is provided with a nanocrystalline structure and/or an ultrafine grain structure; the temperature of the heat treatment is less than or equal to the highest stable existing temperature of the nanocrystalline structure and/or the ultrafine crystal structure in the alloy surface layer;
after severe plastic deformation and heat treatment, the open circuit potential of the alloy surface layer is more negative than that of the alloy matrix;
the alloy matrix comprises one of 7000 series aluminum alloy, austenitic stainless steel, brass and bronze;
when the alloy matrix is 7000 series aluminum alloy, the heat treatment temperature is room temperature-240 ℃;
when the alloy matrix is austenitic stainless steel, the heat treatment temperature is room temperature to 480 ℃;
when the alloy matrix is brass, the heat treatment temperature is room temperature to 550 ℃;
when the alloy matrix is bronze, the heat treatment temperature is room temperature-550 ℃;
when the temperature for heat treatment is room temperature, the time for heat treatment is 1 week to 24 months.
2. A corrosion-inhibiting "sandwich" structure according to claim 1, wherein: the anticorrosion sandwich structure comprises an alloy matrix, an alloy surface layer and a coating; the alloy surface layer and the alloy matrix are consistent in component element type; but the content of at least one element in the alloy surface layer is different from that of the element in the alloy matrix; the alloy surface layer is provided with a nanocrystalline structure and/or an ultrafine grain structure; the thickness of the alloy surface layer is more than or equal to 50 microns.
3. A corrosion-inhibiting "sandwich" structure according to claim 1, wherein: the thickness of the alloy surface layer is 50-500 microns.
4. A corrosion-resistant "sandwich" structure according to claim 1; the method is characterized in that: the severe plastic deformation comprises at least one of shot blasting, ultrasonic shot blasting, sand blasting, laser shot blasting, high pressure water shot blasting, surface mechanical grinding, surface mechanical milling and surface mechanical rolling.
5. A corrosion-resistant "sandwich" structure according to claim 4; the method is characterized in that: during shot blasting, the speed is controlled to be 1-100m/s, the shot blasting grain diameter is controlled to be 1-10mm, and the time is 5-120 min.
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