CN109402450A - A kind of zinc-aluminium magnesium alloy and preparation method thereof of the hot dip containing zr element - Google Patents
A kind of zinc-aluminium magnesium alloy and preparation method thereof of the hot dip containing zr element Download PDFInfo
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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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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Abstract
The present invention relates to metal material corrosion-resistant field, in particular to a kind of zinc-aluminium magnesium alloy and preparation method thereof of the hot dip containing zr element.The hot dip containing zr element is made of with zinc-aluminium magnesium alloy Zn, Al, Mg and Zr element, and each component mass percent is as follows in the alloy: Al:4.0~5.0 wt.%, Mg:0.05~0.15 wt.%, Zr:0.05~0.5 wt.%, surplus Zn.The present invention is by adding suitable zr element into zinc-aluminium magnesium alloy, substantially increase the nucleation rate of alloy, increase the nucleation point of primary phase, the distribution of zinc-rich phase is more uniform, and Zinc-aluminum binary eutectic structure is made to become more tiny and fine and close, the microscopic structure of hot-dip aluminum zinc magnesium alloy has been refined, and has improved the corrosion resistance and resistance to marring of hot-dip aluminum zinc magnesium alloy.
Description
Technical field
The present invention relates to metal material corrosion-resistant field, in particular to a kind of hot dip containing zr element zinc-aluminium magnesium alloy and its
Preparation method.
Background technique
Metal material is easy to happen corrosion during manufacture and use, leads to a large amount of waste of material.Current is main
Steel material aseptic technic has the methods of plating, hot-dip, thermal spraying and spray painting, and hot-dip has as one of method
Unrivaled advantage, such as: the coating of hot dipping plated product and the bond strength of metallic matrix are high, durable protective is strong, immersion plating work
Skill has good adaptability to workpiece shapes and size, and cost is relatively low.Hot dip galvanized zinc alloy coating has been widely used in
Household electrical appliances, building, vehicle ship, petroleum and mechanical and electrical industry.And the wide hot dip galvanized zinc alloy of domestic and international application is main at present
Including Galfan (Zn-5%Al-RE) alloy, Super Zinc (Zn-4.5%Al-0.1%Mg), Galvalume (Al-43.5%
) and ZAM (Zn-6%Al-3%Mg) hot dip galvanized zinc alloy Zn-1.6%Si.
" Super Zinc " alloy is that Nippon Steel research center was developed in 1985, ingredient Zn-4.5%Al-
0.1%Mg.In an atmosphere by ten months exposure experiment it is resulting the result shows that, hot-dip Super Zinc alloy-steel plate ratio
Common hot-dip galvanized steel sheet corrosion resistance is enhanced about more than once, and can partially substitute the pure zine plate of hot-dip.
Studies have shown that Zr element can significantly improve the hardness of fine aluminium, also there is certain refining effect to crystal grain, and can mention
The corrosion resistance of high alloy.Chinese patent retrieval shows: a small amount of titanium, zirconium or rare earth element are added in zinc or aluminium alloy,
The microstructure and comprehensive performance of zinc or aluminium alloy can effectively be improved.
A kind of hot-dip aluminum zinc Mg-Zr alloys of the Chinese invention patent of Publication No. CN103014581B and preparation method thereof
Disclose a kind of hot-dip aluminum zinc Mg-Zr alloys and preparation method thereof, the quality hundred of the various composition of alloy described in the documents
Divide content are as follows: Al4.5-6.5%, Mg3.0-4.0%, Zr0.25-0.75%, surplus Zn, but magnesium in the alloy of the patent disclosure
Too high levels, increase industrial cost, magnesium alloy easily scaling loss at high temperature, stringent to preparation environmental requirement, and content of magnesium is high
Influence coating surface quality, coating surface gray.And content of magnesium difference also results in the alloy structure to be formed difference,
The MgZn of two-fluid is primarily formed when content of magnesium is high2Phase leads to alloy property difference.
Currently, improving the report of Zn-4.5%Al-0.1%Mg alloy for hot-dip, the present invention by addition zr element not yet
By adding suitable zr element in Zn-4.5%Al-0.1%Mg alloy for hot-dip, it was found that a kind of corrosion resistance and scratch resistance
The better dip galvanized aluminum magnesium coating alloy ingredient of property.
Summary of the invention
The object of the present invention is to provide a kind of zinc-aluminium magnesium alloys of the hot dip containing zr element, by zr element with intermediate alloy
Form is added in zinc-aluminium magnesium alloy, for improving the microscopic structure of alloy, and improves its rotproofness and resistance to marring.This hair
It is bright to additionally provide the preparation method of the hot dip galvanized zinc alloy.
For achieving the above object, the technical scheme adopted by the invention is as follows:
A kind of zinc-aluminium magnesium alloy of the hot dip containing zr element, the alloy are made of Zn, Al, Mg and Zr element.
Preferably, hot dip zinc-aluminium Mg-Zr alloys, which is characterized in that each component mass percent is such as in the alloy
Under: Al:4.0~5.0 wt.%, Mg:0.05~0.15 wt.%, Zr:0.05~0.5 wt.%, surplus Zn.
A kind of above-mentioned zinc-aluminium magnesium alloy of the hot dip containing zr element, using following steps:
(1) Zn block, Al block, AlMg intermediate alloy, AlZr intermediate alloy are weighed；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, Al block is placed in crucible, then resistance furnace is heated up
To 700~720 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid；
(4) after Zn block melts completely, AlMg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level or less
To prevent its combustion loss, after its fusing, aluminium alloy is stirred and stands 5~10 minutes, be then added among AlZr
Alloy is simultaneously pressed into zinc-aluminium magnesium melt, and being sufficiently stirred after it melts is uniformly mixed it, and 15~20 points are kept the temperature at 720 DEG C
Clock；
(5) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred；
(6) furnace temperature is down to 500~550 DEG C, the mixed molten liquid after step (5) is refined and removed the gred carries out fishing slag and pours
Casting.
Preferably, it is among AlMg30 that Zn block, Al block purity described in step (1), which are 99.99%, AlMg intermediate alloy,
Alloy, AlZr intermediate alloy are AlZr10 intermediate alloy.
Beneficial effect
The present invention substantially increases the nucleation rate of alloy, makes by adding suitable zr element into hot-dip aluminum zinc magnesium alloy
The nucleation point of primary phase increases, and the distribution of zinc-rich phase is more uniform, and Zinc-aluminum binary eutectic structure is made to become more tiny and cause
It is close, the microscopic structure of hot-dip aluminum zinc magnesium alloy is refined, and improve the corrosion resistance of hot-dip aluminum zinc magnesium alloy and resist
Scratch resistant.
Detailed description of the invention
Fig. 1 is the XRD spectrum of hot dip galvanizing -4.5%Al-0.1%Mg-x%Zr alloy；
Fig. 2 is the stereoscan photograph of hot dip galvanizing -4.5%Al-0.1%Mg alloy (blank sample)；
Fig. 3 is the stereoscan photograph of hot dip galvanizing -4.5%Al-0.1%Mg-0.2%Zr alloy；
Fig. 4 is the stereoscan photograph of hot dip galvanizing -4.5%Al-0.1%Mg-0.5%Zr alloy；
Fig. 5 is the stereoscan photograph of hot dip galvanizing -4.5%Al-0.1%Mg-0.05%Zr alloy；
Fig. 6 is the EDS photo of hot dip galvanizing -4.5%Al-0.1%Mg-0.2%Zr alloy；
Fig. 7 is electrochemical tests of the hot dip galvanizing -4.5%Al-0.1%Mg-x%Zr alloy in 5%NaCl；
Fig. 8 is the coating macro morphology of hot dip galvanizing -4.5%Al-0.1%Mg-x%Zr (x=0,0.5) alloy；
Fig. 9 is the Rockwell hardness curve of hot dip galvanizing -4.5%Al-0.1%Mg-x%Zr coating.
Specific embodiment
Embodiment 1
(1) Zn block, Al block, AlMg intermediate alloy, AlZr intermediate alloy, by mass percentage, alloy have been weighed in proportion
Ingredient are as follows: Al:4.5 wt.%, Mg:0.1 wt.%, Zr:0.2 wt.%, surplus Zn；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, load weighted Al block is placed in crucible, it then will be electric
Resistance furnace is warming up to 720 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid.
(4) after Zn block melts completely, AlMg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level
Below to prevent its combustion loss, aluminium alloy is suitably stirred and stands 5 minutes, AlZr intermediate alloy is then added and is pressed
It is depressed into zinc-aluminium magnesium melt, being sufficiently stirred after it melts is uniformly mixed it, keeps the temperature 15 minutes at 720 DEG C；
(6) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred.
(7) furnace temperature is down to 500 DEG C, the mixed molten liquid after step (6) is refined and removed the gred carries out fishing slag and casting.
The XRD spectrum (Fig. 1) of the hot dip galvanizing -4.5%Al-0.1%Mg-0.2% Zr alloy obtained through the above steps can
To find out, compared with Zn-4.5%Al-0.1%Mg alloy, after Zr element is added, there is Al3Zr phase.By Zn-4.5%Al-0.1%
The stereoscan photograph (Fig. 3) of Mg-0.2% Zr alloy finds out, the microscopic structure of alloy mainly by the rich Zn phase of white, black
α-Al phase, the Zn/Al binary eutectic tissue and Al of lamellar3Zr phase composition.As can be seen that due to Al3The appearance of Zr phase, it is rich
Zinc mutually starts in Al3Zr surrounding growth refines the dendrite of zinc-rich phase, and eutectic structure is also more uniform.
1 position it can be seen from the EDS photo (Fig. 6 a) of hot dip galvanizing -4.5%Al-0.1%Mg-0.2% Zr alloy
The atomic percent of (Fig. 6 b) Al element and Zr element is close to 2:1, and the atom of 2 position (Fig. 6 c) Al elements and Zr element
Percentage is close to 3:1, it is known that this black bulk is Al3Zr phase, and surrounding gray block may due to aluminium segregation and formed
Al2Zr phase, the Zn Elements Atom percentage of 3 positions (Fig. 6 d) are 95.27 at.%, it is known that white petal-shaped is zinc-rich
Phase, 4 position (Fig. 6 e) Zn, Al Elements Atom percentages are respectively 56.04 at.%, 43.70 at.%, it is known where stain
Region is Zn/Al binary eutectoid structure.
Embodiment 2
(1) Zn block, Al block, AlMg intermediate alloy, AlZr intermediate alloy, by mass percentage, alloy have been weighed in proportion
Ingredient are as follows: Al:4.5 wt.%, Mg:0.1 wt.%, Zr:0.5 wt.%, surplus Zn；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, load weighted Al block is placed in crucible, it then will be electric
Resistance furnace is warming up to 700 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid.
(4) after Zn block melts completely, Al-Mg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level
Below to prevent its combustion loss, aluminium alloy is suitably stirred and stands 10 minutes, AlZr intermediate alloy then is added simultaneously
It is pressed into zinc-aluminium magnesium melt, being sufficiently stirred after it melts is uniformly mixed it, keeps the temperature 20 minutes at 720 DEG C；
(6) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred.
(7) furnace temperature is down to 550 DEG C, the mixed molten liquid after step (6) is refined and removed the gred carries out fishing slag and casting.
It the XRD spectrum (Fig. 1) of the hot dip galvanizing -4.5%Al-0.1%Mg-0.5%Zr alloy obtained through the above steps and sweeps
Electromicroscopic photograph (Fig. 4) is retouched as can be seen that the microscopic structure of alloy is mainly by the rich Zn phase of white, the α-Al phase of black, lamellar
Zn/Al binary eutectic tissue and Al3Zr phase composition.
Embodiment 3
(1) Zn block, Al block, AlMg intermediate alloy, AlZr intermediate alloy, by mass percentage, alloy have been weighed in proportion
Ingredient are as follows: Al:4.5 wt.%, Mg:0.1 wt.%, Zr:0.05 wt.%, surplus Zn；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, load weighted Al block is placed in crucible, it then will be electric
Resistance furnace is warming up to 700 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid.
(4) after Zn block melts completely, Al-Mg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level
Below to prevent its combustion loss, aluminium alloy is suitably stirred and stands 7 minutes, AlZr intermediate alloy is then added and is pressed
It is depressed into zinc-aluminium magnesium melt, being sufficiently stirred after it melts is uniformly mixed it, keeps the temperature 18 minutes at 720 DEG C；
(6) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred.
(7) furnace temperature is down to 520 DEG C, the mixed molten liquid after step (6) is refined and removed the gred carries out fishing slag and casting.
Stereoscan photograph (the figure of the hot dip galvanizing -4.5%Al-0.1%Mg-0.05%Zr alloy obtained through the above steps
5) as can be seen that the microscopic structure of alloy is mainly by the rich Zn phase of white, the Zn/Al binary of the α-Al phase of black, lamellar is total
Crystalline substance tissue.
Embodiment 4
(1) Zn block, Al block, AlMg intermediate alloy, AlZr intermediate alloy, by mass percentage, alloy have been weighed in proportion
Ingredient are as follows: Al:4 wt.%, Mg:0.05 wt.%, Zr:0.2 wt.%, surplus Zn；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, load weighted Al block is placed in crucible, it then will be electric
Resistance furnace is warming up to 715 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid.
(4) after Zn block melts completely, Al-Mg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level
Below to prevent its combustion loss, aluminium alloy is suitably stirred and stands 7 minutes, AlZr intermediate alloy is then added and is pressed
It is depressed into zinc-aluminium magnesium melt, being sufficiently stirred after it melts is uniformly mixed it, keeps the temperature 18 minutes at 720 DEG C；
(6) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred.
(7) furnace temperature is down to 520 DEG C, the mixed molten liquid after step (6) is refined and removed the gred carries out fishing slag and casting.
The microscopic structure of alloy manufactured in the present embodiment mainly by white rich Zn phase, the α-Al phase of black, lamellar
Zn/Al binary eutectic tissue and AL3Zr phase composition.
Embodiment 5
(1) Zn block, Al block, AlMg intermediate alloy, AlZr intermediate alloy, by mass percentage, alloy have been weighed in proportion
Ingredient are as follows: Al:5 wt.%, Mg:0.15 wt.%, Zr:0.2 wt.%, surplus Zn；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, load weighted Al block is placed in crucible, it then will be electric
Resistance furnace is warming up to 715 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid.
(4) after Zn block melts completely, Al-Mg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level
Below to prevent its combustion loss, aluminium alloy is suitably stirred and stands 7 minutes, AlZr intermediate alloy is then added and is pressed
It is depressed into zinc-aluminium magnesium melt, being sufficiently stirred after it melts is uniformly mixed it, keeps the temperature 18 minutes at 720 DEG C；
(6) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred.
(7) furnace temperature is down to 520 DEG C, the mixed molten liquid after step (6) is refined and removed the gred carries out fishing slag and casting.
The microscopic structure of alloy manufactured in the present embodiment mainly by white rich Zn phase, the α-Al phase of black, lamellar
Zn/Al binary eutectic tissue and AL3Zr phase composition.
It, can shown in electrochemical tests (Fig. 7) of the hot dip galvanizing -4.5%Al-0.1%Mg-x%Zr alloy in 5%NaCl
To find out the corrosion potential of Zn-4.5%Al-0.1%Mg-0.05%Zr alloy and the corrosion potential of Zn-4.5%Al-0.1%Mg alloy
Difference is little, and the corrosion potential of Zn-4.5%Al-0.1%Mg-0.2%Zr and Zn-4.5%Al-0.1%Mg-0.5%Zr alloy is obvious
Increase, corrosion current significantly reduces, and is substantially better than Zn-4.5%Al-0.1%Mg alloy.Therefore, this Experimental Research, which goes out, works as zirconium
When content is 0.5%, there is more preferable corrosion resistance.
Shown in the macro morphology (Fig. 8) of hot dip galvanizing -4.5%Al-0.1%Mg-x%Zr alloy layer, Zn-4.5%Al-0.1%
" the zinc hammer " on Mg-0.5%Zr hot-dip steel plate surface than Zn-4.5%Al-0.1%Mg hot-dip steel plate surface " zinc hammer " greatly, hot dip
" current mark " of surface of steel plate also becomes apparent, but its surface smoothness is obviously more preferable.
Shown in the Rockwell hardness curve (Fig. 9) of hot dip galvanizing -4.5%Al-0.1%Mg-x%Zr alloy, it can be seen that Zn-
The Rockwell hardness number of 4.5%Al-0.1%Mg alloy for hot-dip is 23.96HRA, and Zn-4.5%Al-0.1%Mg-0.2%Zr hot-dip
The Rockwell hardness number of alloy is 25.32HRA, and when the additive amount of Zr element is 0.5%, Zn-4.5%Al-0.1%Mg hot-dip is closed
The Rockwell hardness number of gold is 26.16 HRA.The result shows that: the Rockwell of Zn-4.5%Al-0.1%Mg-0.5%Zr alloy for hot-dip is hard
Angle value is maximum, and anti-scratch resistance is preferable.Therefore, a certain amount of Zr element is added, the hardness of zinc-aluminium magnesium alloy can be significantly improved,
To improve the resistance to marring of coating.
Comparative example
(1) Zn block, Al block, AlMg intermediate alloy, by mass percentage, the ingredient of alloy are as follows: Al:4.5 have been weighed in proportion
Wt.%, Mg:0.1 wt.%, surplus Zn；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, load weighted Al block is placed in crucible, it then will be electric
Resistance furnace is warming up to 710 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid.
(4) after Zn block melts completely, AlMg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level
Below to prevent its combustion loss, aluminium alloy is suitably stirred and stands 8 minutes, being sufficiently stirred after it melts keeps it mixed
It closes uniformly, keeps the temperature 18 minutes at 720 DEG C；
(6) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred.
(7) furnace temperature is down to 530 DEG C, the mixed molten liquid after step (6) is refined and removed the gred carries out fishing slag and casting.
The XRD spectrum (Fig. 1) and scanning electron microscope of the hot dip galvanizing -4.5%Al-0.1%Mg alloy obtained through the above steps
Photo (Fig. 2) as can be seen that the microscopic structure of alloy mainly by the rich Zn phase of white, the α-Al phase of black and lamellar
Zn/Al binary eutectic tissue composition.
Claims (4)
1. a kind of zinc-aluminium magnesium alloy of the hot dip containing zr element, which is characterized in that the alloy is by Zn, Al, Mg and Zr element group
At.
2. a kind of zinc-aluminium magnesium alloy of the hot dip containing zr element according to claim 1, which is characterized in that in the alloy
Each component mass percent is as follows: Al:4.0~5.0 wt.%, Mg:0.05~0.15 wt.%, Zr:0.05~0.5 wt.%, remaining
Amount is Zn.
3. a kind of preparation method of the zinc-aluminium magnesium alloy of the hot dip containing zr element of any of claims 1 or 2, which is characterized in that
Using following steps:
(1) Zn block, Al block, AlMg intermediate alloy, AlZr intermediate alloy are weighed；
(2) graphite crucible is put and is preheated to kermesinus into resistance furnace, Al block is placed in crucible, then resistance furnace is heated up
To 700~720 DEG C；
(3) Zn block is added after the fusing of Al block, stirs evenly to form allumen liquid；
(4) after Zn block melts completely, AlMg intermediate alloy is added into allumen liquid and is pressed into alloy liquid level or less
To prevent its combustion loss, after its fusing, aluminium alloy is stirred and stands 5~10 minutes, be then added among AlZr
Alloy is simultaneously pressed into zinc-aluminium magnesium melt, and being sufficiently stirred after it melts is uniformly mixed it, and 15~20 points are kept the temperature at 720 DEG C
Clock；
(5) ZnCl is used2Step (4) described ground mixed molten liquid is refined and removed the gred；
(6) furnace temperature is down to 500~550 DEG C, the mixed molten liquid after step (5) is refined and removed the gred carries out fishing slag and pours
Casting.
4. preparation method according to claim 3, which is characterized in that Zn block described in step (1), Al block purity are
99.99%, AlMg intermediate alloy are AlMg30 intermediate alloy, and AlZr intermediate alloy is AlZr10 intermediate alloy.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113046599A (en) * | 2021-03-09 | 2021-06-29 | 保定奥琦圣新型金属材料制造有限公司 | Zinc-aluminum-magnesium alloy ingot for steel strip galvanizing and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113046599A (en) * | 2021-03-09 | 2021-06-29 | 保定奥琦圣新型金属材料制造有限公司 | Zinc-aluminum-magnesium alloy ingot for steel strip galvanizing and preparation method thereof |
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Application publication date: 20190301 |