CN109252125B - Hot-dip galvanized aluminum-magnesium alloy coating and preparation method and application thereof - Google Patents
Hot-dip galvanized aluminum-magnesium alloy coating and preparation method and application thereof Download PDFInfo
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- CN109252125B CN109252125B CN201811276432.XA CN201811276432A CN109252125B CN 109252125 B CN109252125 B CN 109252125B CN 201811276432 A CN201811276432 A CN 201811276432A CN 109252125 B CN109252125 B CN 109252125B
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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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/38—Wires; Tubes
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Abstract
A hot-dip galvanized aluminum-magnesium alloy coating and a preparation method and application thereof are disclosed, the coating comprises the following chemical components, by mass, Zn, Al, Mg, RE = (86.50-98.49), (1-10), (0.5-3), (0.01-0.5), wherein RE is La, Ce or mixed rare earth. The hot-dip galvanized aluminum-magnesium alloy coating for the bridge cable wire has controllable thickness, high adhesive force, difficult peeling and excellent surface quality; the preparation process is simple, no plating leakage is generated, the hot-dip temperature is obviously reduced (from the original temperature of more than 500 ℃ to 420-480 ℃), and the strength loss of the matrix steel wire is controlled within 50 MPa; the corrosion resistance is obviously superior to that of the existing zinc coating and zinc-aluminum alloy coating, the requirement of complex environment on higher comprehensive performance of the bridge cable steel wire is met, and the coating has wide market application prospect.
Description
Technical Field
The invention belongs to the field of steel wire coating and preparation methods thereof, and particularly relates to a hot-dip galvanized aluminum-magnesium alloy coating and a preparation method and application thereof.
Background
With the increase of bridge span and the extension of service life, higher requirements are put forward on the strength and the corrosion resistance of the cable steel wire of the modern bridge. The production process of the high-strength steel wire comprises the following steps: high carbon pearlite steel wire rod → acid cleaning → phosphating → drawing → hot dipping → high strength steel wire product.
Traditionally, bridge cable steel wires are treated by hot galvanizing, and play a role in protecting a matrix by a sacrificial anode, but because the porosity of a zinc layer is high and corrosion products are not compact, a coating has great limitation on the protection of the steel wires. Subsequently, hot-dip galvanized aluminum alloy coatings for second-generation bridge cable steel wires are developed at home and abroad, and although the corrosion resistance is improved, the problems of intergranular corrosion, thicker coatings and the like still exist. In order to meet the new requirements of the design of the bridge for one hundred years, the development of a novel corrosion-resistant coating of the steel wire is urgently needed.
At present, the newly developed third generation hot galvanizing aluminum magnesium alloy coating is mainly used in the automobile steel plate industry, hot dipping is carried out by adopting a protective gas reduction method, the temperature is controlled to be 500-580 ℃, and the corrosion resistance is improved by more than 2 times compared with a zinc-aluminum alloy coating. However, for bridge cable steel wires, the hot-dip temperature is too high, which causes the strength reduction and the torsion performance deterioration of the steel wires, and cannot meet the requirement of the bridge cable structure on the higher comprehensive mechanical properties of the steel wires, so that the hot-dip galvanized aluminum-magnesium alloy coating for preparing the bridge cable steel wires at a lower temperature needs to be developed.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a hot-dip galvanized aluminum-magnesium alloy coating and a preparation method and application thereof, aiming at solving the problem that a bridge cable steel wire simultaneously meets high strength and high corrosion resistance.
The technical scheme is as follows: a hot-dip galvanized aluminum-magnesium alloy coating comprises the following chemical components, by mass, Zn, Al, Mg, RE (86.50-98.49), (1-10), (0.5-3), (0.01-0.5), wherein RE is La, Ce or a mixed rare earth.
The plating layer comprises an alloy layer and a free solidification layer in the thickness direction, the thickness of the alloy layer is not less than 3.0 μm, and the total thickness is 20-120 μm.
The preparation method of the steel wire plated with the hot-dip galvanized aluminum-magnesium alloy coating comprises the following steps: 1) carrying out alkaline washing degreasing treatment, water washing and acid washing rust removal treatment on the surface of the steel wire obtained after drawing, and then drying the steel wire; 2) putting the steel wire obtained in the step 1) into a plating assistant agent solution for plating assistant treatment, wherein the plating assistant agent comprises ZnCl in part by mass2:NH4Cl:SnCl2:KCl:Na3AlF6:CeCl3:H2O (50-200), O (50-150), O (40-160), O (1-30), O (1-20), O (430) and O (857), wherein the plating assisting temperature is 70 ℃, and the time is 60-120 s; 3) drying the steel wire obtained in the step 2) at 100 ℃; 4) the steel wire is taken out for hot dipping after being dried,the chemical components of the plating solution are Zn, Al, Mg, Re (86.50-98.49), 1-10, 0.5-3, 0.01-0.5 by mass percent, the hot-dip temperature is 420-480 ℃, and the hot-dip time is 30-180 s; 5) putting the steel wire obtained in the step 4) into boiling water for cooling for 60 s; 6) and (5) drying the steel wire obtained in the step 5) to obtain a steel wire product.
In the step 1), the steel wire is firstly placed in NaOH solution with the temperature of 70 ℃ and the mass concentration of 15% for degreasing treatment, and then placed in HCl solution with the temperature of 70 ℃ and the mass concentration of 15% for derusting treatment after washing, and then blow-dried.
The chemical composition part ratio of the plating assistant agent in the step 2) is ZnCl2:NH4Cl:SnCl2:KCl:Na3AlF6:CeCl3:H2O100: 95:80:15:10:5: 695; the plating assisting temperature is 70 ℃, and the time is 60-120 s.
And 4) coating an industrial RJ-5 fusing agent on the surface of the plating solution in the step 4).
The hot dip plating in the step 4) adopts single plating by a solvent method.
The hot dip zinc-aluminum magnesium alloy coating is applied to the manufacture of bridge cable steel wires.
Has the advantages that:
1. the hot-dip galvanized aluminum-magnesium alloy coating for the bridge cable wire has controllable thickness, high adhesive force, difficult peeling and excellent surface quality; 2. the preparation process is simple, no plating leakage is generated, the hot-dip temperature is obviously reduced (from the original temperature of more than 500 ℃ to 420-480 ℃), and the strength loss of the matrix steel wire is controlled within 50 MPa; 3. the corrosion resistance is obviously superior to that of the existing zinc coating and zinc-aluminum alloy coating, the requirement of complex environment on higher comprehensive performance of the bridge cable steel wire is met, and the coating has wide market application prospect.
Drawings
FIG. 1 is an electron micrograph of a cross-sectional structure of an alloy plating layer of example 2.
Detailed Description
Example 1:
a hot galvanizing aluminum magnesium alloy coating for bridge cable steel wires comprises the following steps:
(1) and (3) placing the sample steel wire obtained after drawing in a NaOH solution with the temperature of 70 ℃ and the mass concentration of 15% for degreasing, washing with water, placing in an HCl solution with the temperature of 70 ℃ and the mass concentration of 15% for derusting, and drying.
(2) Placing the sample steel wire obtained in the step (1) into a sample steel wire with chemical composition of ZnCl in parts by mass2:NH4Cl:SnCl2:KCl:Na3AlF6:CeCl3:H2And (3) carrying out assistant plating for 120s in an assistant plating solution with the O-ratio of 50:50:40:1:1:1:857, wherein the assistant plating temperature is 70 ℃.
(3) Drying the sample obtained in the step (2) at 100 ℃;
(4) placing the sample steel wire treated in the step (3) in a zinc-aluminum-magnesium alloy solution with the chemical components of Zn, Al, Mg and Ce being 98.49:1:0.5:0.01 in percentage by mass, and carrying out dip plating for 30s at the hot plating temperature of 420 ℃;
(5) putting the sample obtained in the step (4) into boiling water for cooling for 60 s;
(6) and (5) drying the sample obtained in the step (5) to obtain a steel wire product.
Example 2:
a hot galvanizing aluminum magnesium alloy coating for bridge cable steel wires comprises the following steps:
(1) and (3) placing the sample steel wire obtained after drawing in a NaOH solution with the temperature of 70 ℃ and the mass concentration of 15% for degreasing, washing with water, placing in an HCl solution with the temperature of 70 ℃ and the mass concentration of 15% for derusting, and drying.
(2) Placing the sample steel wire obtained in the step (1) into a sample steel wire with chemical composition of ZnCl in parts by mass2:NH4Cl:SnCl2:KCl:Na3AlF6:CeCl3:H2And (3) carrying out assistant plating for 90 seconds in an assistant plating solution with the O-value of 100:95:80:15:10:5:695, wherein the assistant plating temperature is 70 ℃.
(3) Drying the sample obtained in the step (2) at 100 ℃;
(4) placing the sample steel wire treated in the step (3) in a zinc-aluminum-magnesium alloy solution with chemical components of Zn, Al, Mg and Ce being 93.3:5:1.5:0.2 in percentage by mass, and carrying out immersion plating for 90s at the hot-dip plating temperature of 450 ℃;
(5) putting the sample obtained in the step (4) into boiling water for cooling for 60 s;
(6) and (5) drying the sample obtained in the step (5) to obtain a steel wire product.
Example 3:
a hot galvanizing aluminum magnesium alloy coating for bridge cable steel wires comprises the following steps:
(1) and (3) placing the sample steel wire obtained after drawing in a NaOH solution with the temperature of 70 ℃ and the mass concentration of 15% for degreasing, washing with water, placing in an HCl solution with the temperature of 70 ℃ and the mass concentration of 15% for derusting, and drying.
(2) Placing the sample steel wire obtained in the step (1) into a sample steel wire with chemical composition of ZnCl in parts by mass2:NH4Cl:SnCl2:KCl:Na3AlF6:CeCl3:H2And (3) carrying out assistant plating for 60 seconds in an assistant plating solution with the O being 200:150:160:30:20:10:430 at the assistant plating temperature of 70 ℃.
(3) Drying the sample obtained in the step (2) at 100 ℃;
(4) placing the sample steel wire treated in the step (3) in a zinc-aluminum-magnesium alloy solution with the chemical components of Zn, Al, Mg and Ce being 86.5:10:3:0.5 in percentage by mass, and carrying out immersion plating for 180s at the hot-plating temperature of 480 ℃;
(5) putting the sample obtained in the step (4) into boiling water for cooling for 60 s;
(6) and (5) drying the sample obtained in the step (5) to obtain a steel wire product.
Comparative example 1:
the same as example 2, except that the conventional plating assistant agent was used in the preparation method, and the others were not changed.
Comparative example 2:
the same as example 2, except that Mg element was not added to the plating solution, and the rest was not changed.
Comparative example 3:
the same as example 2, except that Al and Mg were not added to the plating solution, and the other elements were not changed.
And (3) performance test results:
the hot dip galvanized aluminum magnesium plated steel wire and each comparative steel wire of the above examples were sampled and subjected to various performance tests, and the results of the tests are shown in table 1.
TABLE 1 measured results of the hot dip galvanized aluminum magnesium plated steel wire and the steel wires of respective comparative examples
In the surface quality test, ○ shows that the surface quality is good and the surface of the steel wire is smooth and bright, x shows that the surface quality is poor and the surface of the steel wire has point and linear slag defects, ○ shows that the plating layer has no plating leakage and is judged to be qualified in the plating leakage test, x shows that the plating layer has plating leakage and is judged to be unqualified, ○ shows that the bent plating layer has no peeling and is judged to be qualified in the bent plating layer test, and x shows that the bent plating layer has peeling and is judged to be unqualified.
From the results in table 1, the corrosion resistance of the coating of examples 1 to 3 of the present invention is gradually improved with the increase of the content of Al, Mg alloy elements, and the corrosion resistance is significantly better than that of the current zinc coating and zinc-aluminum alloy coating; in addition, the coating does not peel off in a bending test, and the surface quality of the coating is good; finally, the strength loss of the matrix steel wire is within 50MPa, and the requirements of the suspension bridge on high strength and high corrosion resistance of the bridge cable steel wire are met.
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.
Claims (1)
1. A preparation method of a hot galvanizing aluminum-magnesium alloy coating for a bridge cable steel wire is characterized by comprising the following steps: (1) placing the sample steel wire obtained after drawing in a NaOH solution with the temperature of 70 ℃ and the mass concentration of 15% for degreasing, washing with water, placing in an HCl solution with the temperature of 70 ℃ and the mass concentration of 15% for derusting, and drying; (2) placing the sample steel wire obtained in the step (1) into a sample steel wire with chemical composition of ZnCl in parts by mass2:NH4Cl:SnCl2:KCl:Na3AlF6:CeCl3:H2In the plating assistant solution with O =50:50:40:1:1:1:857, plating assistant is carried out for 120s, and the plating assistant temperature is 70 ℃; (3) drying the sample obtained in the step (2) at 100 ℃; (4) placing the sample steel wire treated in the step (3) in a zinc-aluminum-magnesium alloy solution with the chemical components of Zn, Al, Mg, Ce =98.49, 1, 0.5, 0.01 in percentage by mass, and carrying out dip plating for 30s at the hot-dip plating temperature of 420 ℃; (5) putting the sample obtained in the step (4) into boiling water for cooling for 60 s; (6) and (5) drying the sample obtained in the step (5) to obtain a steel wire product.
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| CN110004390B (en) * | 2019-05-28 | 2021-12-07 | 无锡市华锋车业部件有限公司 | Zinc-aluminum-magnesium alloy coating and application thereof to steel wire rope for operation |
| CN111197150A (en) * | 2020-02-25 | 2020-05-26 | 李艳华 | Rare earth yttrium zinc aluminum magnesium alloy coating and preparation method thereof |
| CN111647836A (en) * | 2020-06-24 | 2020-09-11 | 东南大学 | Steel wire alloy coating and preparation method and application thereof |
| CN113025845A (en) * | 2020-07-06 | 2021-06-25 | 宝钢集团南通线材制品有限公司 | Zinc-aluminum-magnesium alloy coating steel wire for bridge cable and preparation method thereof |
| CN112410702A (en) * | 2020-11-18 | 2021-02-26 | 国网河南能源互联网电力设计院有限公司 | Plating assistant agent for Zn-Al-Mg-Re alloy and hot dip plating method thereof |
| CN115354192A (en) * | 2022-08-23 | 2022-11-18 | 辛集市澳森金属制品有限公司 | High-strength and high-toughness zinc-aluminum alloy galvanized wire and preparation method thereof |
| CN117702036A (en) * | 2024-02-05 | 2024-03-15 | 天津市辰青金属制品有限公司 | Hot galvanizing method for steel strand inhaul cable for bridge |
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| CN1632157A (en) * | 2003-12-22 | 2005-06-29 | 鞍山钢铁集团公司 | Method for producing zinc-aluminum-magnesium alloy coated steel products with good corrosion resistance and zinc-aluminum-magnesium alloy coated steel products |
| CN103160765A (en) * | 2013-02-20 | 2013-06-19 | 国网智能电网研究院 | Electric transmission line steel member hot-dip galvanizing alloy clad layer and preparation technology thereof |
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| GB2507309A (en) * | 2012-10-25 | 2014-04-30 | Fontaine Holdings Nv | Continuous single dip galvanisation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632157A (en) * | 2003-12-22 | 2005-06-29 | 鞍山钢铁集团公司 | Method for producing zinc-aluminum-magnesium alloy coated steel products with good corrosion resistance and zinc-aluminum-magnesium alloy coated steel products |
| CN103160765A (en) * | 2013-02-20 | 2013-06-19 | 国网智能电网研究院 | Electric transmission line steel member hot-dip galvanizing alloy clad layer and preparation technology thereof |
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