CN104480419A - Plating method of low-aluminum hot-dipped Zn-Al-Mg-Si alloy coating - Google Patents
Plating method of low-aluminum hot-dipped Zn-Al-Mg-Si alloy coating Download PDFInfo
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- CN104480419A CN104480419A CN201410418063.9A CN201410418063A CN104480419A CN 104480419 A CN104480419 A CN 104480419A CN 201410418063 A CN201410418063 A CN 201410418063A CN 104480419 A CN104480419 A CN 104480419A
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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
- 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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- Coating With Molten Metal (AREA)
Abstract
The invention discloses a plating method of a low-aluminum hot-dipped Zn-Al-Mg-Si alloy coating. By the use of an electrolytic activation plating auxiliary, a layer of compact and uniform grey black salt film can be formed on the surface of a protected base material. Thus, the problem that a general plating auxiliary fails when aluminium content is high during hot galvanizing and plating leakage and unevenness happen to the surface of a coating can be solved. By means of a scanning electron microscope and a salt spray test chamber, a microscopic structure and corrosion resistance of a Zn-Al-Mg-Si alloy coating in different composition proportions are measured. It shows through results that a coarse Zn-rich phase can be refined and the structure can be homogenized after proper amounts of Al, Mg and Si are added. Corrosion resistance of the hot-dipped Zn-2%Al-1.5%Mg-0.15%Si alloy coating obtained by the above technological method is optimal.
Description
Technical field
The present invention relates to ferrous materials protection against corrosion field, be specifically related to a kind of plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer.
Background technology
Galvanizing is modal anticorrosion of iron and steel technology, and for improving corrosion resistance nature and the visual appearance of dip galvanized further, people constantly explore and add different-alloy element in zinc liquid, the alloy for hot-dip coating of exploitation excellent performance.Research shows, after adding multiple beneficial alloying element in zinc liquid, due to interaction between alloying element in immersion processes, zinc coating performance has and improves in various degree.Such as, single interpolation Al in zinc liquid, zinc liquid is shinny, and zinc consumption tails off, coating surface light, and coating performance increases; Single interpolation Mg, coating corrosion resistance nature improves, and MgZn appears in coating
2crisp hard phase; If add Al and Mg simultaneously, coating corrosion resistance nature increases substantially, and Zn-MgZn appears in coating
2two component eutectic tissue and Zn-Al-MgZn
2ternary eutectic tissue.More for the research of hot dip galvanizing-Al-Mg alloy layer at present, for developing the alloy for hot-dip coating of corrosion resistance nature and visual appearance excellence, this research by adding Al, Mg, Si simultaneously in zinc liquid, obtain low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer, and its plating technology method and structure property are studied.
Summary of the invention
In order can make when solving aluminium too high levels in pot galvanize, conventional plating assistant agent lost efficacy, the problem such as plating leakage and unfairness appears in coating surface, the invention provides a kind of plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer.
The technical scheme that the present invention takes is:
A plating method for low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer, comprises the steps:
S1, get Q235 steel, economy-combat grinds off except surface scale, cuts into the sample being of a size of 30mm × 30mm × 3mm, preparation hot dip galvanized zinc alloy liquid, the composition of the hot dip galvanized zinc alloy liquid of preparation is Zn-0.5%Al-xMg (x=0,0.5,1.0,1.5wt%), Zn-2%Al-xMg (x=0,0.5,1.0,1.5wt%), Zn-2%Al-1.5%Mg-xSi (x=0,0.15,0.3wt%);
S2, sample is put into concentration is that 150g/L NaOH solution carries out skimming treatment, and the temperature of sodium hydroxide solution is take out after 70-80 DEG C, 1min to put into deionized water and clean;
S3, by the sample after cleaning, to put into massfraction be 15%HCl, and add micro-inhibiter, carry out processing of rust removing, the temperature of hydrochloric acid soln is room temperature, takes out to put into deionized water and clean after 1min;
S4, the sample of step S3 gained put into plating assistant agent solution and carry out electrolytic activation and help plating;
S5, electrolytic activation take out sample after helping plating, put into loft drier and carry out drying and processing, and loft drier temperature is 120 DEG C, and time of drying is 8-10min;
Taken out by sample after S6, sample drying and carry out galvanizing, immersion plating temperature is 460 DEG C-480 DEG C, and the immersion plating time is 1min, before starting to melt, add salt insulating covering agent;
S7, by after step S6 gained sample air cooling 15s, put into pure water and cool.
Wherein, described alloy layer composition is: Al 0.5-2.0%, Mg 0.5-1.5%, Si 0-0.3%, and surplus is Zn.
Wherein, described alloy layer composition is: Al 2%, Mg 1.5%, Si 0.15%, and surplus is Zn.
Wherein, each component concentration of plating assistant agent used in described step S4 is ZnCl by weight percentage
225-30%, NH
4cl 10-15%, NaF 1-2%, Na
3alF
61.5-2.5%, SnCl
21.5-2.5%, CeCl
31-2%, micro-urotropine, all the other are water.
Wherein, in described step S4, electrolytic activation helps the anode of the electrolyzer of plating to be made up of graphite, and negative electrode is made up of body material itself.
Wherein, each component concentration of salt insulating covering agent in described step S6 is by weight percentage: LiCl15-25%, KCl 50-60%, CaCl
215-30%.
The plating aid electrolytic activation that the present invention adopts, can form the grey black salt film of one deck dense uniform at protected substrate surface, conventional plating assistant agent can be made to lose efficacy when can solve aluminium too high levels in pot galvanize, there is the problem such as plating leakage and unfairness in coating surface.Utilize the means such as scanning electronic microscope and salt-mist corrosion tester, determine heterogeneity proportioning Zn-Al-Mg-Si alloy layer microstructure and corrosion resistance nature, result shows, after adding appropriate Al, Mg, Si, and can the thick rich Zn phase of refinement homogenizing tissue; Hot dip galvanizing-2%Al-1.5%Mg-0.15%Si alloy layer the corrosion resistance nature adopting processing method of the present invention to obtain is best.
Accompanying drawing explanation
Fig. 1 is hot dip galvanizing-0.5%Al-xMg (x=0,0.5,1.0,1.5wt%) coating section structure, (a) 0%Mg, (b) 0.5%Mg, (c) 1.0%Mg, (d) 1.5%Mg.
Fig. 2 is hot dip galvanizing-2%Al-xMg (x=0,0.5,1.0,1.5wt%) coating section structure, (a) 0%Mg, (b) 0.5%Mg, (c) 1.0%Mg, (d) 1.5%Mg.
Fig. 3 is hot dip galvanizing-2%Al-1.5%Mg-xSi (x=0.15,0.3wt%) coating section structure, (a) 0.15%Si, (b) 0.3%Si.
The line scanning result of Fig. 4 hot dip galvanizing-2%Al-1.5%Mg-xSi (x=0.15,0.3wt%) alloy layer section structure and each element, (a) 0.15%Si, (b) 0.3%Si
Embodiment
In order to make objects and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiments provide a kind of plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer, comprise the steps:
S1, get Q235 steel, economy-combat grinds off except surface scale, cuts into the sample being of a size of 30mm × 30mm × 3mm, preparation hot dip galvanized zinc alloy liquid, the composition of the hot dip galvanized zinc alloy liquid of preparation is Zn-0.5%Al-xMg (x=0,0.5,1.0,1.5wt%), Zn-2%Al-xMg (x=0,0.5,1.0,1.5wt%), Zn-2%Al-1.5%Mg-xSi (x=0,0.15,0.3wt%);
S2, sample is put into concentration is that 150g/LNaOH solution carries out skimming treatment, and the temperature of sodium hydroxide solution is take out after 70-80 DEG C, 1min to put into deionized water and clean:
S3, by the sample after cleaning, to put into massfraction be 15%HCl, and add micro-inhibiter, carry out processing of rust removing, the temperature of hydrochloric acid soln is room temperature, takes out to put into deionized water and clean after 1min;
S4, the sample of step S3 gained put into plating assistant agent solution and carry out electrolytic activation and help plating;
S5, electrolytic activation take out sample after helping plating, put into loft drier and carry out drying and processing, and loft drier temperature is 120 DEG C, and time of drying is 8-10min;
Taken out by sample after S6, sample drying and carry out galvanizing, immersion plating temperature is 460 DEG C-480 DEG C, and the immersion plating time is 1min, before starting to melt, add salt insulating covering agent;
S7, by after step S6 gained sample air cooling 15s, put into pure water and cool.
Described alloy layer composition is: Al 0.5-2.0%, Mg0.5-1.5%, Si 0-0.3%, and surplus is Zn.
Described alloy layer composition is: Al 2%, Mg 1.5%, Si 0.15%, and surplus is Zn.
The each component concentration of the plating assistant agent used in described step S4 is ZnCl by weight percentage
225-30%, NH
4cl 10-15%, NaF 1-2%, Na
3al F
61.5-2.5%, SnCl
21.5-2.5%, CeCl
31-2%, micro-urotropine, all the other are water.
In described step S4, electrolytic activation helps the anode of the electrolyzer of plating to be made up of graphite, and negative electrode is made up of body material itself.
The each component concentration of salt insulating covering agent in described step S6 is by weight percentage: LiCl 15-25%, KCl 50-60%, CaCl
215-30%.
Embodiment 1
In the present embodiment, in Q235 steel surface heat immersion plating Zn-0.5%Al-xMg (x-=0,0.5,1.0,1.5wt%) alloy layer, alloy layer is prepared adopted plating aid electrolytic activation processing parameter and is: at room temperature carry out, help plating time 100-120s, current density 1.3-1.7A/dm
2; Plating assistant agent composition 25%ZnCl
2, 10%NH
4cl, 1.0%NaF, 1.5%Na
3alF
6, 1.5%SnCl
2, 1.5%CeCl
3, micro-urotropine, all the other are water.
Alkali cleaning (temperature 70-80 DEG C, time 1min, 150g/L NaOH) → washing (deionized water) → pickling (room temperature, time 1min, 15%HCl adds micro-inhibiter) → wash (deionized water) → electrolytic activation to help plating → oven dry (temperature 120 DEG C, time 8-10min) → immersion plating (temperature 460 DEG C ~ 480 DEG C, time 1min) → cooling (after air cooling 15s water-cooled).
Pass through above-mentioned steps, hot dip galvanizing-0.5%Al-xMg (x=0 has been prepared on Q235 steel surface, 0.5,1.0,1.5wt%) alloy layer, as can be seen from this alloy layer macro surface pattern, the coating surface adopting this electrolytic activation to help plating method to prepare is smooth, without defects such as plating leakages; As can be seen from this alloy layer section structure (Fig. 1), along with Mg content increases, the grain refining of coating cross section, eutectic structure region is increasing.
Embodiment 2
In this enforcement, in Q235 steel surface heat immersion plating Zn-2%Al-xMg (x=0,0.5,1.0,1.5wt%) alloy layer, alloy layer is prepared adopted plating aid electrolytic activation processing parameter and is: at room temperature carry out, help plating time 100-120s, current density 1.3-1.7A/dm
2; Plating assistant agent composition 27%ZnCl
2, 10%NH
4cl, 1.5%NaF, 2.0%Na
3alF
6, 2.0%SnCl
2, 2.0%CeCl
3, micro-urotropine, all the other are water.
Alkali cleaning (temperature 70-80 DEG C, time 1min, 150
g/ L NaOH) → washing (deionized water) → pickling (room temperature, time 1min, 15%HCl adds micro-inhibiter) → wash (deionized water) → electrolytic activation to help plating → oven dry (temperature 120 DEG C, time 8-10min) → immersion plating (temperature 460 DEG C ~ 480 DEG C, time 1min) → cooling (after air cooling 15s water-cooled).
Pass through above-mentioned steps, hot dip galvanizing-2%Al-xMg (x=0 has been prepared on Q235 steel surface, 0.5,1.0,1.5wt%) alloy layer, as can be seen from the surperficial macro morphology of this alloy layer, the coating surface adopting this electrolytic activation to help plating method to prepare is level and smooth, without defects such as plating leakages; As can be seen from this alloy layer section structure (Fig. 2), along with Mg content increases, the thick rich zinc phase grain refining of coating cross section, tissue regions homogenizing.
Embodiment 3
In the present embodiment, at Q235 steel surface heat immersion plating Zn-2%Al-1.5%Mg-xSi (x=0.15,0.3wt%) alloy layer, adopted plating aid electrolytic activation processing parameter prepared by alloy layer: at room temperature carry out, help plating time 100-120s, current density 1.3-1.7A/dm
2; Plating assistant agent composition 30%ZnCl
2, 10%NH
4cl, 1.5%NaF, 2.0%Na
3al F
6, 2.0%SnC l
2, 2.0%CeC l
3, micro-urotropine, all the other are water.
Alkali cleaning (temperature 70-80 DEG C, time 1min, 150g/L NaOH) → washing (deionized water) → pickling (room temperature, time 1min, 15%HCl adds micro-inhibiter) → wash (deionized water) → electrolytic activation to help plating → oven dry (temperature 120 DEG C, time 8-10min) → immersion plating (temperature 460 DEG C ~ 480 DEG C, time 1min) → cooling (after air cooling 15s water-cooled).
Hot dip galvanizing-2%Al-1.5%Mg-xSi (x=0.15 has been prepared on Q235 steel surface by above-mentioned steps, 0.3wt%) alloy layer, as can be seen from this alloy layer macro surface pattern, the coating surface adopting this electrolytic activation to help plating method to prepare is level and smooth, without defects such as plating leakages; Known by this alloy layer section structure, add Si and can make coating grain refining.
The present invention utilizes the microstructure and corrosion resistance nature etc. of the means analysis such as scanning electronic microscope and corrosion experiment heterogeneity proportioning Zn-Al-Mg-Si alloy layer.Table 1 is the corrosion experiment result of alloy layer in neutral salt spray, is known by table 1, and when Si content is 0.15%, coating corrosion resistance nature is optimum.
The corrosion experiment result of table 1 alloy layer in neutral salt spray
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a plating method for low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer, is characterized in that, comprise the steps:
S1, get Q235 steel, economy-combat grinds off except surface scale, cuts into the sample being of a size of 30mm × 30mm × 3mm, preparation hot dip galvanized zinc alloy liquid, the composition of the hot dip galvanized zinc alloy liquid of preparation is Zn-0.5%Al-xMg, Zn-2%Al-xMg, Zn-2%Al-1.5%Mg-xSi;
S2, sample is put into concentration is that 150g/L NaOH solution carries out skimming treatment, and the temperature of sodium hydroxide solution is take out after 70-80 DEG C, 1min to put into deionized water and clean;
S3, by the sample after cleaning, to put into massfraction be 15%HCl, and add micro-inhibiter, carry out processing of rust removing, the temperature of hydrochloric acid soln is room temperature, takes out to put into deionized water and clean after 1min;
S4, the sample of step S3 gained put into plating assistant agent solution and carry out electrolytic activation and help plating;
S5, electrolytic activation take out sample after helping plating, put into loft drier and carry out drying and processing, and loft drier temperature is 120 DEG C, and time of drying is 8-10min;
Taken out by sample after S6, sample drying and carry out galvanizing, immersion plating temperature is 460 DEG C-480 DEG C, and the immersion plating time is 1min, before starting to melt, add salt insulating covering agent;
S7, by after step S6 gained sample air cooling 15s, put into pure water and cool.
2. the plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer according to claim 1, it is characterized in that, described alloy layer composition is: Al 0.5-2.0%, Mg 0.5-1.5%, Si 0-0.3%, and surplus is Zn.
3. the plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer according to claim 1, it is characterized in that, described alloy layer composition is: Al 2%, Mg 1.5%, Si 0.15%, and surplus is Zn.
4. the plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer according to claim 1, is characterized in that, each component concentration of the plating assistant agent used in described step S4 is ZnCl by weight percentage
225-30%, NH
4cl 10-15%, NaF 1-2%, Na
3alF
61.5-2.5%, SnCl
21.5-2.5%, CeCl
31-2%, micro-urotropine, all the other are water.
5. the plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer according to claim 1, it is characterized in that, in described step S4, electrolytic activation helps the anode of the electrolyzer of plating to be made up of graphite, and negative electrode is made up of body material itself.
6. the plating method of low aluminothermy immersion plating Zn-Al-Mg-Si alloy layer according to claim 1, it is characterized in that, each component concentration of salt insulating covering agent in described step S6 is by weight percentage: LiCl15-25%, KCl 50-60%, CaCl
215-30%.
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|---|---|---|---|
| CN201410418063.9A CN104480419A (en) | 2014-08-19 | 2014-08-19 | Plating method of low-aluminum hot-dipped Zn-Al-Mg-Si alloy coating |
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Cited By (7)
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|---|---|---|---|---|
| CN105803371A (en) * | 2016-05-25 | 2016-07-27 | 广西民族大学 | Hot galvanizing furnace hearth composite alloy and implementation process |
| CN107587096A (en) * | 2017-10-26 | 2018-01-16 | 济南大学 | A kind of Hot-dip aluminum-silicon zinc yttrium magnesium plating solution and its or immersion |
| CN108463574A (en) * | 2015-12-24 | 2018-08-28 | Posco公司 | Alloy-coated steel plate and its manufacturing method |
| CN110273121A (en) * | 2019-06-12 | 2019-09-24 | 河钢股份有限公司 | Zinc-aluminum-magnesium coated steel strips and preparation method thereof |
| CN113355562A (en) * | 2021-07-05 | 2021-09-07 | 华南理工大学 | Batch hot-dip zinc aluminum magnesium alloy coating and preparation method and application thereof |
| CN113862518A (en) * | 2021-05-12 | 2021-12-31 | 上海大学 | Aluminum-rich zinc-based coating material for reducing brittleness of liquid metal in hot forming process and preparation method thereof |
| US11731397B2 (en) | 2015-12-24 | 2023-08-22 | Posco Co., Ltd | Alloy-coated steel sheet and manufacturing method therefor |
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| CN113355562A (en) * | 2021-07-05 | 2021-09-07 | 华南理工大学 | Batch hot-dip zinc aluminum magnesium alloy coating and preparation method and application thereof |
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