CN113969381A - Chloride ion corrosion resistant coating and preparation method and application thereof - Google Patents

Chloride ion corrosion resistant coating and preparation method and application thereof Download PDF

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Publication number
CN113969381A
CN113969381A CN202111253989.3A CN202111253989A CN113969381A CN 113969381 A CN113969381 A CN 113969381A CN 202111253989 A CN202111253989 A CN 202111253989A CN 113969381 A CN113969381 A CN 113969381A
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alloy
chloride ion
aluminum
preparation
resistant coating
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CN113969381B (en
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张先满
李星涛
陈再雨
季坤鹏
罗洪峰
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Hainan University
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Hainan 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The invention belongs to the field of novel materials, and discloses a chloride ion corrosion resistant coating, a preparation method and application thereof, wherein the coating is made of Fe2Al5Simple substance Si phase, boride containing Al and lamellar structure. And carrying out hot dip aluminum plating-diffusion heat treatment on the prepared Fe-Cr-Si-B alloy so as to prepare the metal coating with the complex structure. During the corrosion process of the plating layer in NaCl solution, the lamellar structure is preferentially dissolved and then reaches Fe2Al5Both phases function as sacrificial anodes. The preparation method is simple in preparation process, and the prepared metal coating is compact, well combined with a substrate and has excellent chloride ion corrosion resistance.

Description

Chloride ion corrosion resistant coating and preparation method and application thereof
Technical Field
The invention relates to the field of novel materials, in particular to a chloride ion corrosion resistant coating and a preparation method and application thereof.
Background
Corrosion leads to material failure, serious hazards, and significant economic losses. And the chloride ions in the seawater are easy to cause pitting corrosion, and influence the service life of the ocean engineering equipment. The existing marine anticorrosion technology mainly adopts the physical barrier effect of organic coatings such as epoxy resin and the like for protection, but the density and the integrity of the coating are difficult to guarantee, the bonding force with a substrate is weak, and the coating is easy to age by illumination and radiation. Researchers have also developed research on the improvement of chloride ion corrosion resistance by metal coatings, and the related technologies include thermal spraying, chemical vapor deposition, hot dipping and the like. The hot dip coating mainly comprises hot dip galvanizing, hot dip aluminizing and hot dip galvanizing-aluminum alloy. The basic principle is to utilize the sacrificial anode effect of the residual zinc or aluminum layer on the metal surface. However, during the hot dip coating process, an intermetallic compound layer consisting of Fe-Zn or Fe-Al is also formed at the solid-liquid interface between the steel and the molten metal. Since the outer layer is covered with the residual metal, there are few reports of improving the resistance of the steel substrate to chloride ion corrosion by using the intermetallic compound.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a chloride ion corrosion resistant coating and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a chloride ion corrosion resistant coating, said coating comprising Fe2Al5Simple substance Si phase, boride containing Al and lamellar structure.
A preparation method for preparing the chloride ion corrosion resistant coating comprises the following steps:
(1) preparation of Fe-Cr-Si-B alloy
Preparing a Fe-Cr-Si-B alloy having a B content of 7.0 to 9.0 wt.%, a Cr content of 15.0 to 25.0 wt.%, an Si content of 0 to 10.0 wt.%, a C content of 0.2 to 0.5 wt.%, and the balance Fe;
(2) hot dip aluminizing
Immersing the Fe-Cr-Si-B alloy prepared in the step (1) into aluminum liquid, carrying out hot dip aluminum plating, reacting for a certain time, quickly extracting a sample from the aluminum liquid, and carrying out air cooling to obtain the Fe-Cr-Si-B alloy with aluminum attached to the surface;
(3) diffusion heat treatment
Heating the Fe-Cr-Si-B with aluminum attached to the surface prepared in the step (2) at 700-1000 ℃, keeping the temperature for 8-24h, and cooling along with the furnace; obtaining the chloride ion corrosion resistant coating.
The preparation of the Fe-Cr-Si-B alloy in the step (1) comprises the following steps:
proportioning: calculating the required micro-carbon ferrochrome (Fe-58 wt.% Cr-0.06 wt.% C), Fe-18 wt.% B, Fe-45 wt.% Si master alloy and pig iron weight according to the designed alloy composition;
smelting: and (3) after the weighed raw materials in the step I are completely melted, pouring to obtain the Fe-Cr-Si-B alloy casting.
The Fe-Cr-Si-B alloy in the step (1) has simple substance Si phase and Fe in the structure3Si phase, ferrite and boride.
The temperature of the aluminum liquid in the step (2) is 700-900 ℃, preferably 750 ℃, and the hot dip coating time is 10-25 min, preferably 15 min;
the aluminum liquid in the step (2) can be pure Al or a mixture of Al and at least one alloy element of Zn, Mg, Si and the like.
The shape, components and position of the simple substance Si phase are kept unchanged in the hot dip aluminum plating and diffusion heat treatment processes.
The boride remains unchanged in position during hot dip aluminum plating and diffusion heat treatment, but contains more Al element and gradually changes into a lamellar structure.
The application of the chloride ion corrosion resistant coating in preparing a chloride ion corrosion resistant material.
During the corrosion process of the plating layer by NaCl solution, the lamellar structure is preferentially dissolved.
The shape, the components and the position of the simple substance Si phase are kept unchanged in the NaCl solution corrosion process.
Compared with the prior art, the invention has the following beneficial effects:
1. the metal coating with complex components is generated in situ by hot dip aluminum plating and diffusion heat treatment, the process is simple, the coating is compact, and the binding force with a matrix is strong.
2. The lamellar structure in the coating is preferentially corroded to Fe2Al5Both of them can play the role of sacrificial anode to protect the steel matrix.
Drawings
FIG. 1 is a microstructure of Fe-Cr-Si-B alloy prepared in example 1.
FIG. 2 shows the interface morphology of the Fe-Cr-Si-B alloy prepared in example 1 after hot dip aluminum plating-diffusion heat treatment.
FIG. 3 is an interface morphology of the hot-dip aluminized-diffusion heat-treated Fe-Cr-Si-B alloy prepared in example 1 after corrosion by a NaCl solution.
FIG. 4 shows the interface morphology of the hot-dip aluminized-diffusion heat-treated Fe-Cr-Si-B alloy prepared in example 2 after corrosion by NaCl solution.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited to these examples.
The Fe-Cr-Si-B alloy in the examples was prepared by the following method:
proportioning: calculating the weight of required micro-carbon ferrochrome (Fe-58 wt.% Cr-0.06 wt.% C), Fe-18 wt.% B, Fe-45 wt.% Si intermediate alloy and pig iron according to the designed alloy components, wherein the total weight is 10 kg;
smelting: and (3) putting the weighed raw materials in the step I into a vacuum smelting furnace, and pouring the raw materials into a sand mold after the raw materials are completely molten to obtain the Fe-Cr-Si-B alloy casting.
Example 1:
(1) an Fe-Cr-Si-B alloy of Fe-15.3 wt.% Cr-10.0 wt.% Si-8.5 wt.% B-0.4 wt.% C was prepared, the microstructure of which is shown in FIG. 1 and can be seen to consist of ferrite, boride, Fe3Si and simple substance Si phase.
(2) Carrying out hot dip aluminum plating on the Fe-Cr-Si-B alloy, wherein the aluminum liquid is pure aluminum, the temperature of the aluminum liquid is 750 ℃, the hot dip plating time is 15 minutes, and the sample is taken out and then emptiedCooling, performing diffusion heat treatment at 750 deg.C, keeping the temperature for 8 hr, taking out, and air cooling to room temperature. The cross-sectional structure is shown in FIG. 2 and is made of Fe2Al5Simple substance Si phase, boride containing Al and lamellar structure.
(3) Immersing the sample prepared in step (2) into a 5 wt.% NaCl solution for 9 days. The cross section structure is shown in figure 3, the lamellar structure is corroded preferentially, and the simple substance Si phase is stable.
Example 2:
(1) an Fe-Cr-Si-B alloy of Fe-15.3 wt.% Cr-10.0 wt.% Si-8.5 wt.% B-0.4 wt.% C with a structure consisting of ferrite, boride, Fe is prepared3Si and simple substance Si phase.
(2) Carrying out hot dip aluminum plating on the Fe-Cr-Si-B alloy, wherein the aluminum liquid is pure aluminum, the temperature of the aluminum liquid is 750 ℃, the hot dip plating time is 15 minutes, taking out the sample, air-cooling, carrying out diffusion heat treatment again, the temperature is 750 ℃, keeping the temperature for 2 hours, taking out, air-cooling to the room temperature. The cross-sectional structure of the alloy consists of Fe2Al5Simple substance Si phase, boride containing Al and lamellar structure.
(3) Immersing the sample prepared in step (2) into a 5 wt.% NaCl solution for 1 day. The cross section structure is shown in figure 4, the Al remained on the outer layer is preferentially corroded, the lamellar structure is corroded, and the simple substance Si phase is stable.
Example 3:
(1) the structure of the Fe-Cr-B alloy which contains 15.3 wt.% of Cr, 8.5 wt.% of B and 0.5 wt.% of C consists of ferrite and boride.
(2) Carrying out hot dip aluminum plating on the Fe-Cr-Si-B alloy, wherein the aluminum liquid is pure aluminum, the temperature of the aluminum liquid is 750 ℃, the hot dip plating time is 15 minutes, taking out the sample, air-cooling, carrying out diffusion heat treatment again, the temperature is 750 ℃, keeping the temperature for 2 hours, taking out, air-cooling to the room temperature. The cross-sectional structure of the alloy consists of Fe2Al5Boride containing Al and lamellar structure.
(3) Immersing the sample prepared in step (2) into a 5 wt.% NaCl solution for 2 days. The residual Al layer on the outer layer is preferentially corroded.
The above-mentioned embodiments are preferred embodiments of the present invention, and the present invention is not limited thereto, and any other modifications or equivalent substitutions that do not depart from the technical spirit of the present invention are included in the scope of the present invention.

Claims (8)

1. A chloride ion corrosion resistant coating, characterized in that said coating comprises Fe2Al5Simple substance Si phase, boride containing Al and lamellar structure.
2. A method for preparing the chloride ion corrosion-resistant coating of claim 1, comprising the steps of:
(1) preparation of Fe-Cr-Si-B alloy
Preparing a Fe-Cr-Si-B alloy having a B content of 7.0 to 9.0 wt.%, a Cr content of 15.0 to 25.0 wt.%, an Si content of 0 to 10.0 wt.%, a C content of 0.2 to 0.5 wt.%, and the balance Fe;
(2) hot dip aluminizing
Immersing the Fe-Cr-Si-B alloy prepared in the step (1) into aluminum liquid, carrying out hot dip aluminum plating, reacting for a certain time, quickly extracting a sample from the aluminum liquid, and carrying out air cooling to obtain the Fe-Cr-Si-B alloy with aluminum attached to the surface;
(3) diffusion heat treatment
Heating the Fe-Cr-Si-B with aluminum attached to the surface prepared in the step (2) at 700-1000 ℃, keeping the temperature for 8-24h, and cooling along with the furnace; obtaining the chloride ion corrosion resistant coating.
3. The method according to claim 2, wherein the Fe-Cr-Si-B alloy of step (1) is prepared by:
proportioning: calculating the weight of Fe-58 wt.% Cr-0.06 wt.% C, Fe-18 wt.% B, Fe-45 wt.% Si intermediate alloy and pig iron required by the designed alloy composition;
smelting: and (3) after the weighed raw materials in the step I are completely melted, pouring to obtain the Fe-Cr-Si-B alloy casting.
4. The method according to claim 2, wherein said Fe-Cr-Si-B alloy of step (1)The structure of the alloy contains simple substance Si phase and Fe3Si phase, ferrite and boride.
5. The method of claim 2, wherein: and (3) the temperature of the aluminum liquid in the step (2) is 700-900 ℃, and the hot dipping time is 10-25 min.
6. The method of claim 2, wherein: and (3) the molten aluminum in the step (2) is pure Al or a mixture of Al and at least one alloy element of Zn, Mg and Si.
7. Use of a chloride ion corrosion resistant coating according to claim 1 for the preparation of a chloride ion corrosion resistant material.
8. Use according to claim 7, characterized in that: during the corrosion process of the plating layer by NaCl solution, the lamellar structure is preferentially dissolved;
the shape, the components and the position of the simple substance Si phase are kept unchanged in the NaCl solution corrosion process.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN115141994A (en) * 2022-07-07 2022-10-04 海南大学 Multilayer films with etch anisotropy comprising novel quaternary MAB phases and methods of making and etching the same
CN115418592A (en) * 2022-08-01 2022-12-02 海南大学 Chloride molten salt corrosion resistant coating and preparation method thereof

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CN108588507A (en) * 2018-06-15 2018-09-28 广州宇智科技有限公司 The novel hot-dip plating aluminium alloy of resistance to hydrogen sulfide and chlorination sodium corrosion

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Publication number Priority date Publication date Assignee Title
CN115141994A (en) * 2022-07-07 2022-10-04 海南大学 Multilayer films with etch anisotropy comprising novel quaternary MAB phases and methods of making and etching the same
CN115418592A (en) * 2022-08-01 2022-12-02 海南大学 Chloride molten salt corrosion resistant coating and preparation method thereof
CN115418592B (en) * 2022-08-01 2023-06-27 海南大学 Chloride molten salt corrosion resistant coating and preparation method thereof

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