CN102146536A - High-corrosion resistant zinc-based complex alloy and smelting preparation process thereof - Google Patents
High-corrosion resistant zinc-based complex alloy and smelting preparation process thereof Download PDFInfo
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- CN102146536A CN102146536A CN2011101193084A CN201110119308A CN102146536A CN 102146536 A CN102146536 A CN 102146536A CN 2011101193084 A CN2011101193084 A CN 2011101193084A CN 201110119308 A CN201110119308 A CN 201110119308A CN 102146536 A CN102146536 A CN 102146536A
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Abstract
The invention provides a high-corrosion resistant zinc-based complex alloy and a smelting preparation process thereof. The high-corrosion resistant zinc-based complex alloy is mainly used for hot-dip surface treatment processes of steel components for improving the corrosion resistance of the components. The technical scheme is that: the total amount of alloying elements is controlled within 1.0 percent by adjusting and optimizing the dosage and the proportion of the zinc base and the alloying elements such as Al, RE, Mg, Si and the like; therefore, the corrosion resistance of a hot-dip zinc-based alloy coating is improved; high dip-plating performance of an alloy melt is ensured; and the fluidity and the wetting quality of alloy plating solution are further improved. The zinc-based complex alloy has the components in percentage by mass: 0.5 to 0.6 percent of the Al, 0.2 to 0.3 percent of the RE (La, Ce and Pr-mixed rear earth), 0.01 to 0.02 percent of the Si, 0.01 to 0.02 percent of the Mg and the balance of the Zn. The preparation process flow for the zinc-based complex alloy comprises the following steps of: weighing and dosing pure zinc, pure aluminium, a rare earth aluminum alloy, an aluminium silicon alloy and an aluminium magnesium alloy serving as raw materials according to the mass percentage of each of the elements in the zinc-based complex alloy; and preparing the zinc-based complex alloy by the processes such as heating, smelting, stirring, keeping temperature, deslagging, casting and the like respectively.
Description
Technical field
The present invention relates to a kind of high anticorrosive zinc base multicomponent alloy and melting preparation technology thereof, be mainly used in iron and steel parts hot dip process surface treatment procedure,, belong to metallic substance preparation and manufacture field to improve the part corrosion resistance nature.
Background technology
The loss that corrosion causes iron and steel is extremely serious, and according to incompletely statistics, 1/3 of the annual output of steel in the whole world loses because of corrosion, and only the direct economic loss that causes at the annual invar iron rot of China just reaches and exceeds 100 billion.Corrosion not only brings enormous economic loss, also can cause heavy loss of life and personal injury.Therefore, be necessary to study the corrosion prevention measure of iron and steel, and pot galvanize is acknowledged as one of the most direct effective means of iron and steel protection.
Pot galvanize is with the immersion plating regular hour in the fused zinc of certain temperature is bathed of the iron and steel after handling, and taking out the cooling back, obtain one deck on the surface attractive in appearance and have the technology of good corrosion resistance protective layer.In recent years, the production of China's metallic zinc all occupies first place in the world with consumption, and demand rises year by year, and market potential is big.According to the consumption structure analysis of world's zinc in 2006, the whole world 0
#50% of zinc is used for pot galvanize.
Along with the day of expanding economy and metals resources is becoming tight, the pot galvanize product also will develop to characteristics such as diversification, high-performance, low consumption.For this reason, continually develop a series of high performance hot-dip galvanized alloy coating both at home and abroad.
Existing achievement in research both domestic and external shows, adds alloying element in zinc is bathed, and can obviously improve the galvanizing production quality, reduce production costs.
Al is the known raising zinc coating the most effective corrosion proof alloying element.Can be divided into low aluminium (Al＜5%) and high alumina (Al＞5%) two big series to Zn-Al alloy according to the addition of Al in zinc.
Containing aluminium during zinc is bathed is 0.005%～0.020% o'clock, can significantly improve the coating light, reduces zinc and bathes surface oxidation.During aluminium content in zinc is bathed＞0.15%, at first can on iron-based, form one deck successive Fe-Al layer mutually, suppress the growth of Fe-Zn reaction and fragility Fe-Zn alloy phase layer, make coating attenuate and adhesion good, about 0.2% Al amount is applicable to the continuous hot galvanizing of band steel and steel wire.At present, the above-mentioned technology that adds small amount of aluminum in zinc is bathed has been widely used in the pot galvanize field, plays the effect that improves the coating visual appearance, reduces production costs.But such coating is because Al content is low, and the tissue of free zinc layer and solidity to corrosion there is no obvious change.
When the Al addition surpassed 1%, solidity to corrosion improved effect and begins obviously, and best results when Al content reaches 4～7% further increases with Al content later on, and the zn-al alloy coating solidity to corrosion descends on the contrary.So the Al about 5% for improving the zinc coating solidity to corrosion, is low Al is best composition in the Zn-Al alloy.The hot dip process that increases to of aluminium content had brought the immersion plating poor-performing during but zinc was bathed, and occurred problems such as plating leakage phenomenon easily, had increased the operational difficulty of immersion plating, caused the immersion plating product percent of pass to decline to a great extent.
When the content of aluminium continues to raise, the corrosion resisting property of Zn-Al alloy can be improved significantly, especially aluminium content reaches at 55% o'clock, such coating can use under more complicated corrosive environment, but the immersion plating performance of this kind coating is poorer, can't use traditional plating assistant agent, the plating assistant agent prescription that therefore plates pre-treatment becomes the gordian technique that needs solution.
In addition, in zinc and zinc alloy, add trace rare-earth element, can improve its solidity to corrosion and various mechanical propertys etc.Rare earth has purification, degasification, the removal of impurity, crystal grain thinning, reinforcement matrix and improves effects such as processing characteristics in metallic substance.
International Lead and Zinc Study Group and Liege, Belgium Centre De Recherches Metallurgiques have successfully developed a kind of novel Zn-Al-RE alloy hot-dip coating in 1980, the chemical ingredients of this alloy layer is 5%Al-0.1%RE-Zn.Compare with zinc coating, this alloy layer has better solidity to corrosion, and formability, tack are also relatively good, but also has the problem of immersion plating difficulty.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing galvanizing and the existence of zinc alloy technology, a kind of high anticorrosive zinc base multicomponent alloy and melting preparation technology thereof are provided, by regulating and optimize the consumption and the proportioning of Zn base and Al, RE, alloying elements such as Mg, Si, with the overall control of alloying element in 1.0%, both improved the solidity to corrosion of hot dipping zinc-base alloy layer, guarantee that again alloy melt has immersion plating performance preferably, the flowability of alloy electroplating bath and wetting property are further improved.
The quality percentage composition of the various compositions of Zinc-based multi-element alloy of the present invention is: Al 0.5～0.6%, RE (La, Ce, Pr mishmetal) 0.2～0.3%, Si 0.01～0.02%, Mg 0.01～0.02%, surplus is Zn.
Preparation technology's flow process of this Zinc-based multi-element alloy is:
A, fine aluminium, rare earth aluminium alloy, aluminum silicon alloy, aluminum magnesium alloy are carried out weighing and batching according to the mass ratio of various elements in Zinc-based multi-element alloy of the present invention, be heated to 650 ℃ with its fusing with smelting furnace, stir, insulation is more than 1 hour;
B, calculate and weighing residue zinc amount according to the mass ratio of each element in the Zinc-based multi-element alloy of the present invention, be heated to 450 ℃ with its fusing with smelting furnace, stir, insulation is more than 1 hour;
C, the prepared zinc liquation of B step is poured in the prepared alloy liquation of A step, stirred, insulation is more than 1 hour, and naturally cools to 450 ℃, remove slag after casting make Zinc-based multi-element alloy.
Used raw material is commercial pure zinc, fine aluminium, rare earth aluminium alloy (La, Ce, Pr mishmetal), aluminum silicon alloy, aluminum magnesium alloy among the above-mentioned preparation technology.
The effect of each component is embodied in this Zinc-based multi-element alloy: elements such as (1) Al, Si can significantly improve hot-dip coated solidity to corrosion, wherein Al plays a major role, the adding of Si mainly is to play the collaborative corrosion proof effect that improves with Al, can reduce the addition of Al, guarantee that again coating has good solidity to corrosion simultaneously.(2) rare earth element such as La, Ce, Pr and Mg can improve the hot dip condition, plating bath flowability, wetting property are greatly improved, surface zinc can be bathed by faster backflow zinc when plating piece proposed the zinc bath, thereby make coating more smooth, smooth, reduce the appearance that coating surface drips defectives such as knurl and current mark, can significantly reduce simultaneously the thickness of zinc layer, thereby reduce the zinc consumption, reduce production costs.
The present invention compares with zinc alloy with zinc ingot metal with existing hot dip has following advantage and effect: (1) corrosion resisting property is good, is 70～90 hours through the neutral salt spray corrosion test rust time, improves more than 20% than pure zinc coating; (2) immersion plating excellent property, smooth surface, smooth, defectives such as no plating leakage, dross and current mark; (3) versatility is good, in whole technical process of hot dip process to the workpiece substrate pre-treatment, help each operations such as plating, immersion plating, passivation not have particular requirement, adopt traditional galvanized equipment and the processing condition can be at steel-iron components surface immersion plating new zinc based multicomponent alloy; (4) metal wastage is little, and thickness of coating only is 40～50 μ m, compares traditional zinc coating and has reduced more than 20%; (5) economic benefit is obvious, because the usage quantity of various alloying elements is all lower, therefore the cost of material of galvanizing based multicomponent alloy is not compared with pure zinc and can be surpassed 5%, but coating performance can improve 20%, metal wastage can reduce by 20%, therefore uses this Zinc-based multi-element alloy immersion plating cost performance of product to be higher than galvanizing far away.
Description of drawings
Fig. 1 is the melting preparation technology schema of the high anticorrosive zinc base multicomponent alloy of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
1) prepare Zinc-based multi-element alloy by following composition: Al 0.5%, RE (La, Ce, Pr mishmetal) 0.2%, Si 0.02%, Mg 0.01%, surplus is Zn.Raw materials used commercial pure zinc, fine aluminium, Al-80%RE alloy (La, Ce, Pr mishmetal), Al-10%Si alloy, the Al-5%Mg alloy of being.
2) prepare the 100Kg Zinc-based multi-element alloy through following technical process, standby:
A, calculate according to the mass ratio of various elements in Zinc-based multi-element alloy of the present invention, difference weighing Al-80%RE alloy 0.25Kg, Al-10%Si alloy 0.2Kg, Al-5%Mg alloy 0.2Kg and fine aluminium 0.08Kg, then these raw materials are mixed, be heated to 650 ℃ with its fusing with smelting furnace, stir, insulation is more than 1 hour;
B, weighing residue zinc amount 99.27Kg are heated to 450 ℃ with its fusing with smelting furnace, stir, and insulation is more than 1 hour;
C, the prepared zinc liquation of B step is poured in the prepared alloy liquation of A step, stirred, insulation is more than 1 hour, and naturally cools to 450 ℃, remove slag after casting make required Zinc-based multi-element alloy.
3) with this Zinc-based multi-element alloy steel-iron components is carried out hot dip process: the mild steel plate with 100mm * 60mm * 2mm is carrying out degrease, washing, pickling, washing and plating assistant agent processing earlier, drop into an amount of Zinc-based multi-element alloy in the immersion plating groove then and be heated to 450 ℃, after treating that metal melts fully in the groove, steel plate is immersed maintenance taking-up in about 1 minute in the groove, immerse again and clean in the tank and cool off, immerse traditional galvanizing inactivating liquid at last workpiece is carried out Passivation Treatment, water is clean with workpiece cleaning after the passivation, promptly finishes all immersion plating technology flow processs.
4) even, the light, smooth of the steel plate outward appearance after immersion plating Zinc-based multi-element alloy and Passivation Treatment, through technology for detection, thickness of coating is about 40 μ m, and the neutral salt spray corrosion test rust time is 70～75 hours, corrosion resisting property surpasses pure zinc coating 20%, satisfies application requiring fully.
Embodiment 2
1) prepare Zinc-based multi-element alloy by following composition: Al 0.55%, RE (La, Ce, Pr mishmetal) 0.24%, Si 0.015%, Mg 0.015%, surplus is Zn.Raw materials used commercial pure zinc, fine aluminium, Al-80%RE alloy (La, Ce, Pr mishmetal), Al-10%Si alloy, the Al-5%Mg alloy of being.
2) use the method identical with embodiment 1 to be prepared into the 100Kg Zinc-based multi-element alloy, the consumption of various raw materials is pure zinc 99.18Kg, fine aluminium 0.07Kg, Al-80%RE alloy (La, Ce, Pr mishmetal) 0.3Kg, Al-10%Si alloy 0.15Kg, Al-5%Mg alloy 0.3Kg.
3) use the method identical to iron and steel parts immersion plating Zinc-based multi-element alloy and Passivation Treatment with embodiment 1.
4) even, the light, smooth of the steel plate outward appearance after immersion plating Zinc-based multi-element alloy and Passivation Treatment, through technology for detection, thickness of coating is about 45 μ m, and the neutral salt spray corrosion test rust time is 75～80 hours, corrosion resisting property surpasses pure zinc coating 30%, satisfies application requiring fully.
Embodiment 3
1) prepare Zinc-based multi-element alloy by following composition: Al 0.6%, RE (La, Ce, Pr mishmetal) 0.3%, Si 0.01%, Mg 0.02%, surplus is Zn.Used raw materials used commercial pure zinc, fine aluminium, Al-80%RE alloy (La, Ce, Pr mishmetal), Al-10%Si alloy, the Al-5%Mg alloy of being.
2) use the method identical with embodiment 1 to be prepared into the 100Kg Zinc-based multi-element alloy, the consumption of various raw materials is pure zinc 99.07Kg, fine aluminium 0.055Kg, Al-80%RE alloy (La, Ce, Pr mishmetal) 0.375Kg, Al-10%Si alloy 0.1Kg, Al-5%Mg alloy 0.4Kg.
3) use the method identical to iron and steel parts immersion plating Zinc-based multi-element alloy and Passivation Treatment with embodiment 1.
4) even, the light, smooth of the steel plate outward appearance after immersion plating Zinc-based multi-element alloy and Passivation Treatment, through technology for detection, thickness of coating is about 50 μ m, and the neutral salt spray corrosion test rust time is 80～90 hours, corrosion resisting property surpasses pure zinc coating 40%, satisfies application requiring fully.
Claims (2)
1. one kind high anticorrosive zinc base multicomponent alloy and melting preparation technology thereof, the quality percentage composition that it is characterized in that the various compositions of this multicomponent alloy is: Al 0.5～0.6%, RE (La, Ce, Pr mishmetal) 0.2～0.3%, Si 0.01～0.02%, Mg 0.01～0.02%, surplus is Zn.
2. a kind of high anticorrosive zinc base multicomponent alloy as claimed in claim 1 and melting preparation technology thereof is characterized in that this multicomponent alloy is prepared by following technical process:
A, commercial fine aluminium, rare earth aluminium alloy, aluminum silicon alloy, aluminum magnesium alloy are carried out weighing and batching according to the mass ratio of various elements in Zinc-based multi-element alloy of the present invention, be heated to 650 ℃ with its fusing with smelting furnace, stir, insulation is more than 1 hour;
B, calculate and weighing residue zinc amount, commercial pure zinc is heated to 450 ℃ with its fusing with smelting furnace, stir, be incubated more than 1 hour according to the mass ratio of each element in the Zinc-based multi-element alloy of the present invention;
C, the prepared zinc liquation of B step is poured in the prepared alloy liquation of A step, stirred, insulation is more than 1 hour, and naturally cools to 450 ℃, remove slag after casting make Zinc-based multi-element alloy.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113046673A (en) * | 2021-03-11 | 2021-06-29 | 江苏中远稀土新材料有限公司 | Corrosion-resistant rare earth multi-element alloy coating for steel cable bridge |
| CN113652722A (en) * | 2021-08-19 | 2021-11-16 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium alloy ingot and method for producing uniform zinc-aluminum-magnesium plating solution |
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| CN101818316A (en) * | 2010-05-11 | 2010-09-01 | 昆明理工大学 | Zinc-based multi-element alloy for hot dipping and preparation method thereof |
| WO2011025042A1 (en) * | 2009-08-31 | 2011-03-03 | 新日本製鐵株式会社 | High-strength hot-dip galvanized steel sheet and process for producing same |
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Patent Citations (2)
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| WO2011025042A1 (en) * | 2009-08-31 | 2011-03-03 | 新日本製鐵株式会社 | High-strength hot-dip galvanized steel sheet and process for producing same |
| CN101818316A (en) * | 2010-05-11 | 2010-09-01 | 昆明理工大学 | Zinc-based multi-element alloy for hot dipping and preparation method thereof |
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Cited By (3)
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| CN113046673A (en) * | 2021-03-11 | 2021-06-29 | 江苏中远稀土新材料有限公司 | Corrosion-resistant rare earth multi-element alloy coating for steel cable bridge |
| CN113652722A (en) * | 2021-08-19 | 2021-11-16 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium alloy ingot and method for producing uniform zinc-aluminum-magnesium plating solution |
| CN113652722B (en) * | 2021-08-19 | 2022-12-27 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium alloy ingot and method for producing uniform zinc-aluminum-magnesium plating solution |
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Application publication date: 20110810 |