CN115141994A - Multilayer films with etch anisotropy comprising novel quaternary MAB phases and methods of making and etching the same - Google Patents
Multilayer films with etch anisotropy comprising novel quaternary MAB phases and methods of making and etching the same Download PDFInfo
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- CN115141994A CN115141994A CN202210795713.6A CN202210795713A CN115141994A CN 115141994 A CN115141994 A CN 115141994A CN 202210795713 A CN202210795713 A CN 202210795713A CN 115141994 A CN115141994 A CN 115141994A
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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
- C23C2/06—Zinc or cadmium or alloys based thereon
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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
- C23C2/12—Aluminium or alloys based thereon
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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
- C23C2/26—After-treatment
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Abstract
The present invention provides a multilayer film comprising a novel quaternary MAB phase having corrosion anisotropy, the multilayer film comprising FeAl, and methods of making and etching the same 3 Two intermetallic compounds with quaternary MAB phase, feAl 3 And the distribution is alternated with the quaternary MAB. The multilayer film and the preparation method thereof are simple, the prepared multilayer film is compact and well combined with a substrate, the corrosion path can be prolonged, the corrosion resistance time is prolonged, and the steel substrate can be well protected.
Description
Technical Field
The invention relates to the field of novel materials, in particular to a multi-layer film with corrosion anisotropy and containing a novel quaternary MAB phase, and a preparation method and a corrosion method thereof.
Background
Corrosion is a kind of damage which occurs silently, and materials, especially metal materials, are subject to severe corrosion, thereby shortening the service life thereof. The search for new antiseptic techniques and methods is urgent but far from. Compared with the metal integral material with improved corrosion resistance, the surface treatment has the advantages of low cost, rapidness, high efficiency and the like. Therefore, surface treatment technologies such as organic coating, metal spraying, hot dipping and the like can be widely applied in the field of seawater corrosion prevention. Among them, the multilayer film plays a very important role. Generally, the multilayer film is mainly prepared by methods such as electrodeposition, 3D printing and the like, and the defects such as bonding force between layers, holes, residual stress and the like are difficult to solve, so that the further improvement of the corrosion resistance of the multilayer film is limited.
The MAB (M = Cr, mo, and other transition metal elements, a = Al element, and B = B element) phase is a novel layered structure material, has excellent corrosion resistance, high temperature oxidation resistance, and other properties, and has recently received much attention from researchers. The existing MAB phases mainly comprise: cr (chromium) component 2 AlB 2 、Cr 3 AlB 4 、Cr 4 AlB 6 And ternary MAB phases such as MoAlB. Also in small amounts such as (Mo) 2/3 Sc 1/3) AlB 2 、(Mo 2/3 Y 1/3 )AlB 2 The reports of the quaternary MAB phase are characterized in that M in the quaternary MAB phase is replaced by different transition group metal elements, the preparation process is complex and the cost is high.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel quaternary MAB phase-containing multilayer film with corrosion anisotropy, and a preparation method and a corrosion method thereof, which can prolong the corrosion path, prolong the corrosion resistance time and protect a steel matrix.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: multilayer film with corrosion anisotropy comprising novel quaternary MAB phases comprising FeAl 3 Two intermetallic compounds with quaternary MAB phase, feAl 3 Alternating with quaternary MABs.
In a preferred scheme, the quaternary MAB phase is a Cr-Al-Zn-B intermetallic compound, and A comprises Al and Zn.
In a preferred embodiment, the FeAl is 3 The multilayer film composed of quaternary MAB phase is continuously covered on the steel matrix, is not interrupted, and is approximately parallel to the matrix.
The invention also provides a preparation method of the multilayer film with corrosion anisotropy and containing the novel quaternary MAB phase, which comprises the following steps:
step one, preparation: preparing Fe-Cr-B cast steel;
step two, hot dip coating: immersing the Fe-Cr-B cast steel obtained in the step one into a Zn-xAl alloy melt for hot dip coating reaction, then extracting a sample, air-cooling, and generating a continuous multilayer film consisting of two intermetallic compounds alternately on a solid-liquid reaction interface, wherein the Zn-xAl alloy is attached to the outside of the multilayer film;
step three, mechanical grinding: and D, polishing the surface of the Fe-Cr-B cast steel comprising the multilayer film prepared in the step two, and polishing and removing the Zn-xAl alloy attached to the outside of the multilayer film.
In a preferred scheme, in the first step, the casting sand mold is placed on a chill internally filled with cooling water for directional solidification, and the directional solidification preparation of the Fe-Cr-B cast steel is completed.
In a preferred embodiment, the prepared cast Fe-Cr-B steel comprises (Cr, fe) 2 B phase and Fe matrix, (Cr, fe) 2 The phase B and the Fe matrix are in columnar parallel distribution in the vertical direction.
In a preferred scheme, in the second step, the value range of x in the Zn-xAl alloy is 40 to 90wt.%.
In a preferred scheme, in the second step, the hot dip coating reaction time is 10 to 30min, and the reaction temperature is 700 to 800 ℃.
The invention also provides a corrosion method of the multilayer film with the corrosion anisotropy and containing the novel quaternary MAB phase, which comprises the steps of embedding and wrapping a sample of the multilayer film with the corrosion anisotropy and containing the novel quaternary MAB phase by using denture powder, only leaving one surface exposing the multilayer film, and then placing the sample in a constant-temperature NaCl solution for corrosion.
The multilayer film containing the novel quaternary MAB phase and having the corrosion anisotropy, and the preparation and corrosion methods thereof have the following beneficial effects:
1. in the Cr-Al-Zn-B quaternary MAB phase, A = Al and Zn, which is different from the prior quaternary MAB phase in which M is replaced by different transition group metal elements, and the energy of the MAB phase is reduced and is more stable by alloying A. In addition, the quaternary MAB phase of Cr-Al-Zn-B is different from the ternary MAB phase of Cr-Al-B, and A in the ternary MAB phase of Cr-Al-B is Al. Thus, a = Al, zn also broadens the material system of the MAB phase.
2. Preparing Fe-Cr-B cast steel by directional solidification, performing hot dip coating on Zn-xAl alloy, and generating FeAl on a solid-liquid interface in situ 3 The continuous multilayer film alternately consists of two intermetallic compounds Cr-Al-Zn-B, and has compact structure, no defect and high adhesion to the base.
3. Quaternary Cr-Al-Zn-B intermetallics exhibit corrosion inertness, whereas FeAl 3 The steel substrate is dissolved preferentially, and the corrosion process is subjected to the periodic development of transverse development → longitudinal penetration → transverse development → longitudinal penetration, so that the corrosion path is prolonged, the corrosion time is prolonged, and the steel substrate is protected.
4. In the corrosion process, zn and Al in the Cr-Al-Zn-B quaternary MAB phase are selectively precipitated, so that the corrosion resistance of the alloy is further improved.
Drawings
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
FIG. 1 is a schematic view of a directional solidification apparatus used in the present invention;
FIG. 2 is a microstructure of a multilayer film prepared in example 1;
FIG. 3 is a graph showing the distribution of Cr, al, zn elements in the multilayer film prepared in example 1;
FIG. 4 is a cross-sectional structure of the multi-layer film prepared in example 1 after being corroded by NaCl solution;
fig. 5 is a microstructure view of the multilayer film prepared in example 2.
Detailed Description
The Fe-Cr-B cast steel in the examples was prepared by the following method:
(1) preparing materials: the required micro-carbon ferrochrome Fe-58wt.% Cr-0.06wt.% C, fe-18 wt wt.% B, fe-45 wt wt.% Si master alloy and pig iron weight were calculated for the designed alloy composition, with a total weight of 10kg.
(2) Smelting: and (2) loading the raw materials weighed in the step (1) into a vacuum smelting furnace.
(3) Directional solidification: pouring the molten iron in the step (2) into a directional solidification device shown in figure 1, and placing a sand mold into a cooling device with cooling water introduced thereinOn iron so that the solidification order is formed from bottom to top and in the vertical direction (Cr, fe) 2 The phase B and the Fe matrix are in columnar parallel distribution structure and cooled to room temperature.
Example 1:
step one, immersing the prepared Fe-Cr-B cast steel into Zn-60 wt percent Al alloy melt for hot dipping reaction, wherein the melt temperature is 750 ℃, the hot dipping time is 30 minutes, taking out a sample, and then cooling by air to prepare a novel quaternary MAB phase-containing multilayer film, wherein the cross section microstructure of the novel quaternary MAB phase is shown in figure 2, and FeAl can be seen 3 The intermetallic compound and the Cr-Al-Zn-B quaternary MAB are alternately formed into a multilayer film.
The surface distribution of Cr, al and Zn elements in the multilayer film is shown in FIG. 3.
And manually grinding the surface residual Zn-60 wt% Al alloy layer by using a sand paper grinding mode.
Step two, the sample prepared in the step one is immersed into 3.5 wt% NaCl solution for 3 days to be corroded. Specifically, the sample prepared in the first step was embedded with denture powder to cover 5 surfaces, leaving only one surface of a special structure consisting of two different intermetallic compounds exposed to a constant temperature NaCl solution.
The cross-sectional structure is shown in FIG. 4, feAl 3 Preferential corrosion, while the Cr-Al-Zn-B intermetallic compound shows corrosion inertness, and the corrosion process undergoes the periodic development of transverse development → longitudinal penetration → transverse development → longitudinal penetration, showing corrosion anisotropy.
Example 2:
step one, performing hot dip coating on the prepared Fe-Cr-B cast steel with Zn-90 wt percent of Al, wherein the melt temperature is 750 ℃, the hot dip coating time is 15 minutes, taking out a sample, then performing air cooling, and generating FeAl on an interface 3 A multi-layer film composed of two intermetallic compounds of Cr-Al-Zn-B, as shown in FIG. 5. And manually grinding the surface residual Zn-90 wt% Al alloy layer by using a sand paper grinding mode.
Step two, immersing the sample prepared in the step one into 3.5 wt% NaCl solution to corrode for 5 days, and FeAl 3 Preferentially corrode, whereas the Cr-Al-Zn-B intermetallic compounds of the MAB phase exhibit corrosion inertness.
Example 3:
step one, performing hot dip coating on the prepared Fe-Cr-B cast steel with Zn-80 wt percent of Al melt at the temperature of 750 ℃ for 10 minutes, taking out a sample, performing air cooling, and generating FeAl on an interface 3 And a multilayer film composed of two intermetallic compounds of Cr-Al-Zn-B. And manually grinding the surface residual Zn-80 wt% Al alloy layer by a sand paper grinding mode.
Step two, the sample prepared in step one is immersed into 3.5 wt% NaCl solution for 7 days to be corroded. FeAl 3 Preferentially corrode, whereas the Cr-Al-Zn-B intermetallic compounds of the MAB phase exhibit corrosion inertness.
Claims (9)
1. A multilayer film having corrosion anisotropy comprising a novel MAB phase comprising FeAl 3 Two intermetallic compounds with quaternary MAB phase, feAl 3 Alternating with quaternary MABs.
2. The multilayer film having corrosion anisotropy comprising a novel quaternary MAB phase, according to claim 1, wherein said quaternary MAB phase is a Cr-Al-Zn-B intermetallic, A comprises Al and Zn.
3. The multilayer film having corrosion anisotropy comprising a novel quaternary MAB phase, as claimed in claim 1, wherein the FeAl phase 3 The multi-layer film composed of the quaternary MAB phase continuously covers the steel substrate without interruption and is distributed approximately parallel to the substrate.
4. A method for preparing a multilayer film having corrosion anisotropy and comprising a novel quaternary MAB phase, comprising the steps of:
step one, preparation: preparing Fe-Cr-B cast steel;
step two, hot dip coating: immersing the Fe-Cr-B cast steel obtained in the step one into a Zn-xAl alloy melt for hot dip coating reaction, then extracting a sample, air-cooling, and generating a continuous multilayer film consisting of two intermetallic compounds alternately on a solid-liquid reaction interface, wherein the Zn-xAl alloy is attached to the outside of the multilayer film;
step three, mechanical grinding: and D, polishing the surface of the Fe-Cr-B cast steel comprising the multilayer film prepared in the step two, and polishing and removing the Zn-xAl alloy attached to the outside of the multilayer film.
5. The method for preparing a multilayer film containing a novel quaternary MAB phase with corrosion anisotropy as claimed in claim 4, wherein, in the first step, the casting sand mold is placed on a chill internally filled with cooling water for directional solidification, and the directional solidification preparation of the Fe-Cr-B cast steel is completed.
6. The method of claim 5, wherein the Fe-Cr-B cast steel comprises (Cr, fe) 2 B phase and Fe matrix, (Cr, fe) 2 The phase B and the Fe matrix are in columnar parallel distribution in the vertical direction.
7. The method for preparing a multilayer film with corrosion anisotropy and containing a novel quaternary MAB phase as claimed in claim 4, wherein in the second step, the value of x in the Zn-xAl alloy ranges from 40 to 90wt.%.
8. The method for preparing a multilayer film with corrosion anisotropy and containing a novel quaternary MAB phase as claimed in claim 4, wherein in the second step, the hot dip coating reaction time is 10 to 30min, and the reaction temperature is 700 to 800 ℃.
9. A method for corroding a multi-layer film with corrosion anisotropy and containing a novel quaternary MAB phase is characterized in that a sample of the multi-layer film with corrosion anisotropy and containing the novel quaternary MAB phase is embedded and wrapped by denture powder, only one surface of the multi-layer film is exposed, and then the sample is placed in a constant-temperature NaCl solution for corrosion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210795713.6A CN115141994A (en) | 2022-07-07 | 2022-07-07 | Multilayer films with etch anisotropy comprising novel quaternary MAB phases and methods of making and etching the same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210795713.6A CN115141994A (en) | 2022-07-07 | 2022-07-07 | Multilayer films with etch anisotropy comprising novel quaternary MAB phases and methods of making and etching the same |
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Citations (7)
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|---|---|---|---|---|
| CN102292464A (en) * | 2009-01-16 | 2011-12-21 | 新日本制铁株式会社 | Hot-dip Zn-Al-Mg-Si-Cr alloy coated steel material with excellent corrosion resistance |
| CN103543060A (en) * | 2012-07-09 | 2014-01-29 | 中国石油化工集团公司 | Corrosion sample inlaying method |
| JP2016153539A (en) * | 2016-06-01 | 2016-08-25 | Ｊｆｅ鋼板株式会社 | MOLTEN Al-Zn-BASED PLATED SHEET STEEL AND PRODUCTION METHOD THEREOF |
| CN107385374A (en) * | 2017-09-01 | 2017-11-24 | 海南大学 | Inserted double coatings of intermetallic compound ceramics in a kind of original position and preparation method thereof |
| CN111334723A (en) * | 2020-03-10 | 2020-06-26 | 西安交通大学 | Zinc liquid cavitation erosion resistant cast Fe-B alloy and preparation method thereof |
| CN111549295A (en) * | 2020-05-14 | 2020-08-18 | 北京工业大学 | Fe-B alloy resisting zinc liquid erosion abrasion and preparation method thereof |
| CN113969381A (en) * | 2021-10-27 | 2022-01-25 | 海南大学 | Chloride ion corrosion resistant coating and preparation method and application thereof |
-
2022
- 2022-07-07 CN CN202210795713.6A patent/CN115141994A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102292464A (en) * | 2009-01-16 | 2011-12-21 | 新日本制铁株式会社 | Hot-dip Zn-Al-Mg-Si-Cr alloy coated steel material with excellent corrosion resistance |
| CN103543060A (en) * | 2012-07-09 | 2014-01-29 | 中国石油化工集团公司 | Corrosion sample inlaying method |
| JP2016153539A (en) * | 2016-06-01 | 2016-08-25 | Ｊｆｅ鋼板株式会社 | MOLTEN Al-Zn-BASED PLATED SHEET STEEL AND PRODUCTION METHOD THEREOF |
| CN107385374A (en) * | 2017-09-01 | 2017-11-24 | 海南大学 | Inserted double coatings of intermetallic compound ceramics in a kind of original position and preparation method thereof |
| CN111334723A (en) * | 2020-03-10 | 2020-06-26 | 西安交通大学 | Zinc liquid cavitation erosion resistant cast Fe-B alloy and preparation method thereof |
| CN111549295A (en) * | 2020-05-14 | 2020-08-18 | 北京工业大学 | Fe-B alloy resisting zinc liquid erosion abrasion and preparation method thereof |
| CN113969381A (en) * | 2021-10-27 | 2022-01-25 | 海南大学 | Chloride ion corrosion resistant coating and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIANMAN ZHANG等: "Effects of Cr and Zn on the interfacial microstructures of borides in Fe-Cr-B cast steels during hot-dipping in Al-Zn alloys"", vol. 110, no. 3, pages 202 - 205 * |
| 王天元等: "定向凝固 Fe-18%Cr-3%B-Si 合金组织及高温抗氧化性能", vol. 50, no. 11, pages 271 - 272 * |
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