CN1632157A - Method for producing zinc-aluminum-magnesium alloy coated steel products with good corrosion resistance and zinc-aluminum-magnesium alloy coated steel products - Google Patents
Method for producing zinc-aluminum-magnesium alloy coated steel products with good corrosion resistance and zinc-aluminum-magnesium alloy coated steel products Download PDFInfo
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- CN1632157A CN1632157A CN 200310119444 CN200310119444A CN1632157A CN 1632157 A CN1632157 A CN 1632157A CN 200310119444 CN200310119444 CN 200310119444 CN 200310119444 A CN200310119444 A CN 200310119444A CN 1632157 A CN1632157 A CN 1632157A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 62
- 239000010959 steel Substances 0.000 title claims abstract description 62
- -1 zinc-aluminum-magnesium Chemical compound 0.000 title claims abstract description 37
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000005260 corrosion Methods 0.000 title claims description 20
- 230000007797 corrosion Effects 0.000 title claims description 20
- 238000007747 plating Methods 0.000 claims abstract description 71
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000011592 zinc chloride Substances 0.000 abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 1
- 235000019270 ammonium chloride Nutrition 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007716 flux method Methods 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
The present invention discloses a process for preparing zincium aluminum-magnesium alloy plating steel products and zincium aluminum-magnesium alloy plating steel products. A solvent method and a gas fluid reduction method are adopted, wherein the chemical components of the plating solution is 2.5-20% of AL, 1.5-4.5% of Mg, 0.01-0.3% of RE, with the rest being Zn and unavoidable impurities; right amount of Si and V are added into the plating solution, wherein the solvent is aqueous solution with a chemical composition of 200-1000g/L ZnCl2, 0-200g/L NH4Cl, 0-100g/L KCl, 0-100g/L NaCl and 0-100g/L rare earth chloride, with the pH being 3-4; the temperature of the plating solution is controlled at 450-580 DEG C, and the plating time is 2-300s. The present invention improves the moisturising capacity for steel products, restrains the reaction of aluminum and chlorides solvents, and then avoids plating leakage occurring and improves the bonding force of plating layers, not only can produce sheet materials but also can produce plating steel products such as sectional materials, pipes and wire rods, and have wide extending and applying foreground.
Description
Technical field
The invention belongs to the galvanizing field, zinc-aluminum-magnesium alloy layer steel and production method that particularly a kind of solidity to corrosion is good.
Background technology
In the galvanizing field; in order to improve the solidity to corrosion of galvanized steel; zinc 5% aluminium, 0.06% rare earth alloy electroplated steel products (commodity are called Galfan), zinc 55% aluminium, 1.6% silicon alloy electroplated steel products (commodity are called Galvalume) have been developed; but zinc 5% aluminium 0.06% rare earth alloy only improves 2 times～3 times of solidity to corrosions; though zinc 55% aluminium 1.6% silicon has significantly improved solidity to corrosion, has lost the galvanic protection performance of zinc.US3505043, spy the zinc-aluminum-magnesium alloy layer steel that flat 10-226865, spy open flat 11-193452 and provide are provided have been significantly improved solidity to corrosion; and owing to used magnesium; the galvanic protection performance is good; but because aluminium content; make that the alloy layer of coating is thicker; and the production technique of the zinc-aluminum-magnesium alloy layer that more than provides generally all adopts the gas reduction method, adopts the gas reduction method can only be applied to being coated with steel.
Also having a kind of method in the alloy layer technology of steel is flux method, when adopting flux method to produce, generally all be applied to the production of pure zinc (or in the zinc single alloying element content＜5%) electroplated steel products, because its solidity to corrosion of this product requirement is good, the content of its magnalium is than higher, the poor ability of the wetting base steel of production process interalloy easily produces plating leakage.And because the bath temperature of zinc-aluminum-magnesium is low, it is 450 ℃～580 ℃, can not use dystectic fluorous solvent that contains, can only use low-melting chlorinated solvent, aluminium in the plating bath has precedence over zinc and chlorinated solvent effect, generates lower boiling aluminum chloride, at steel substrate surface a large amount of bubbles takes place, make the bonding force variation of coating and base steel, the qualification rate of product is lower.Therefore up to the present do not find to produce the example of zinc-aluminum-magnesium electroplated steel products as yet with flux method.
Summary of the invention
In order to solve the problem that exists when gas reduction method and flux method are produced zinc-aluminum-magnesium alloy layer steel, the invention provides zinc-aluminum-magnesium alloy layer steel production method and zinc-aluminum-magnesium alloy layer steel.
Its production technique of the present invention is, employing be degreasing-washing-pickling-be coated with the technology of solvent-oven dry-hot dip process-air cooling, it is characterized in that,
A) Chemical Composition of its plating bath is Al 2.5%～20%, and Mg 1.5%～4.5%, and RE 0.01%～0.3%, and all the other are Zn and unavoidable impurities;
B) its solvent is the aqueous solution, and chemical constitution is ZnCl
2200g/l～1000g/l, NH
4Cl 0g/l～200g/l, KCl 0g/l～100g/l, NaCl 0g/l～100g/l, rare earth chloride 0g/l～100g/l, the pH of solvent are 3～4;
C) temperature of plating bath is controlled at 450 ℃～580 ℃, and plating piece residence time in plating bath is 2s～300s.
The another kind of processing method that the present invention adopts is, the technology of uncoiling-welding-(degreasing)-annealing-temperature adjustment-hot dip process-air knife wiping-cool off-batch is characterized in that,
A) Chemical Composition of its plating bath is Al 2.5%～20%, and Mg 1.5%～4.5%, and RE 0.01%～0.3%, and all the other are Zn and unavoidable impurities;
B) temperature of being with steel to go into the zinc pot is 480 ℃～520 ℃, and the temperature of plating bath is controlled at 470 ℃～520 ℃, and plating piece residence time in plating bath is 2s～30s, and air knife pressure is 2kPa～80kPa, plating postcooling speed＞1 ℃/s.
The chemical constitution of using its coating of zinc-aluminum-magnesium alloy layer steel of above-mentioned processing method production is by weight percentage: Al 2.5%～20%, and Mg 1.5%～4.5%, RE (mishmetal) 0.01%～0.2%, and all the other are Zn and unavoidable impurities.
In order to improve the tissue of alloy layer, in the solution of producing zinc-aluminum-magnesium alloy layer steel, add Si 0.01%～0.5%, V0.0001%～0.2%, the chemical constitution of its its coating of zinc-aluminum-magnesium alloy layer steel is by weight percentage: Al 2.5%～20%, Mg 1.5%～4.5%, RE (mishmetal) 0.01%～0.2%, Si 0.01%～0.5%, and all the other are Zn and unavoidable impurities for V0.0001%～0.2%.
The concrete chemical constitution of solvent of the present invention has ZnCl
2600～800g/l, NH
4Cl0～200g/l, KCl 0～100g/l, NaCl 0～100g/l, rare earth chloride 0g/l～100g/l, the pH of solvent is controlled at 3～4.
Production technique of the present invention goes for the hot dip process of different steel.
The invention provides a kind of solidity to corrosion good zinc-aluminum-magnesium electroplated steel products and production method, the content of aluminium, magnesium, rare earth, silicon, vanadium in the control plating bath, and adopted solvent method and the gas reduction method of being coated with, improved the wetting ability of plating bath to steel, suppressed the reaction of aluminium and chlorinated solvent, thereby avoided the generation of plating leakage, improved the bonding force of coating, improved product percent of pass, not only can produce sheet material, can also produce electroplated steel products such as section bar, tubing, wire rod, have broad prospect for its application.
Specific embodiment
Its production technique of the present invention is, employing be degreasing-washing-pickling-be coated with technology of solvent-oven dry-hot dip process-air cooling,
A) Chemical Composition of its plating bath is Al 2.5%～20%, and Mg 1.5%～4.5%, and RE 0.01%～0.3%, and all the other are Zn and unavoidable impurities;
B) its solvent is the aqueous solution, and chemical constitution is ZnCl
2200g/l～1000g/l, NH
4Cl 0g/l～200g/l, KCl 0g/l～100g/l, NaCl 0g/l～100g/l, rare earth chloride 0g/l～100g/l, the pH of solvent is controlled at 3～4;
C) temperature of plating bath is controlled at 450 ℃～580 ℃, and plating piece residence time in plating bath is 2s～300s.
The another kind of processing method that the present invention adopts is, uncoiling-welding-(degreasing)-annealing-temperature adjustment-hot dip process-air knife wiping-sky but-technology of batching, it is characterized in that,
A) Chemical Composition of its plating bath is Al 2.5%～20%, and Mg 1.5%～4.5%, and RE 0.01%～0.3%, and all the other are Zn and unavoidable impurities;
B) temperature of being with steel to go into the zinc pot is 480 ℃～520 ℃, and the temperature of plating bath is controlled at 470 ℃～520 ℃, and plating piece residence time in plating bath is 2s～30s, and air knife pressure is 2kPa～80kPa, plating postcooling speed＞1 ℃/s.
The chemical constitution of using its coating of zinc-aluminum-magnesium alloy layer steel of above-mentioned processing method production is by weight percentage: Al 2.5%～20%, and Mg 1.5%～4.5%, RE (mishmetal) 0.01%～0.2%, and all the other are Zn and unavoidable impurities.
In order to improve the tissue of alloy layer, in the solution of producing zinc-aluminum-magnesium alloy layer steel, add Si 0.01%～0.5%, V 0.0001%～0.2%, the chemical constitution of its its coating of zinc-aluminum-magnesium alloy layer steel is by weight percentage: Al 2.5%～20%, Mg 1.5%～4.5%, RE (mishmetal) 0.01%～0.2%, and Si 0.01%～0.5%, V0.0001%～0.2%, all the other are Zn and unavoidable impurities.
The concrete chemical constitution of solvent of the present invention has ZnCl
2600g/l～800g/l, NH
4Cl0g/l～200g/l, KCl 0g/l～100g/l, NaCl 0g/l～100g/l, rare earth chloride 0g/l～100g/l, the pH of solvent is controlled at 3～4.
When shaped steel was carried out hot dip process, its bath temperature was 450 ℃～560 ℃, and plating piece residence time in plating bath is 45s～300s.
Steel wire is carried out hot dip process, and its bath temperature is 450 ℃～520 ℃, and plating piece residence time in plating bath is 10s～60s.
Steel plate, band steel are carried out hot dip process, and its bath temperature is 470 ℃～530 ℃, and plating piece residence time in plating bath is 10s～60s.
Aluminium content＜2.5% o'clock in the coating, the solidity to corrosion of electroplated steel products is poor, aluminium content＞20% o'clock, the galvanic protection poor performance of electroplated steel products.
Mg content in the coating＜1.5% o'clock, the solidity to corrosion of electroplated steel products is poor, Mg content＞4.5% o'clock, the ductility of electrodeposited film of electroplated steel products is poor.
Coating middle-weight rare earths content＜0.01% o'clock easily produces plating leakage, can not suppress the reaction of aluminium and chlorinated solvent fully, content of rare earth＞0.2% o'clock, and the easy oxidation of the solution of alloy generates a large amount of scum silica frost, is difficult to plating.
Content of rare earth in the plating bath is controlled at 0.02%～0.3% reason, rare earth enters the coating except part, also part enters cadmia, the partial oxidation loss, and plating bath middle-weight rare earths content was less than 0.02% o'clock, can not guarantee that coating middle-weight rare earths content reaches 0.01%, content of rare earth＞0.3% o'clock, coating middle-weight rare earths content＞0.2%, the easy oxidation of plating bath, generate a large amount of scum silica frost, be difficult to plating.
Silicon did not reduce the effect of alloy layer thickness less than 0.01% o'clock in the plating bath, and silicon was greater than 0.5% o'clock in the plating bath, and its effect that reduces alloy layer thickness reaches capacity.
Vanadium is less than 0.0001% in the plating bath, can not suppress because of adding the acicular structure that silicon produces, or can not refinement coating tissue, vanadium was greater than 0.2% o'clock in the plating bath, and its effect that improves the coating tissue reaches capacity.
When zinc chloride content is less than 200g/l in the solvent, can not generate complete protective membrane at steel surface, the easy oxidation of steel surface, the bonding force of coating is poor; When zinc chloride content is greater than 1000g/l in the solvent, excessive at the protective membrane thickness that steel surface forms, be difficult for breaking away from and being difficult for from plating bath, floating from plating piece, the surface quality of plating piece is reduced.
When other muriate and zinc chloride were used in the solvent, it is best that the effect of solvent reaches.
The pH of solvent was less than 3 o'clock, and the corrodibility of solvent is strong, easily generated iron(ic) chloride, made the tack of solvent and helped the plating deleterious, and the pH of solvent was greater than 4 o'clock, and the solvent facile hydrolysis lost efficacy.
When bath temperature was lower than 450 ℃, the chemically reactive of plating bath was low, and is insufficient with the reaction of base steel, and the bonding force of coating is poor, easily produces plating leakage.When bath temperature is higher than 580 ℃, the easy oxidation of plating bath, oxide compound easily sticks on the coating, and the surface quality of coating is reduced.
Coating composition provided by the invention, bath element and bath temperature can also be used for the gas reduction method and produce continuous belt steel, in the occasion that zinc-aluminum-magnesium coating band steel processing characteristics is had relatively high expectations, can also in coating, use 0.01%～0.5% Si, to reduce the thickness of alloy layer, can also use 0.0001%～0.2% V, with crystal grain thinning and the abnormal structure that avoids producing because of adding Si.
Claims (9)
1, the production method of the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion is good, employing be degreasing-washing-pickling-be coated with the technology of solvent-oven dry-hot dip process-air cooling, it is characterized in that,
A) Chemical Composition of its plating bath is Al2.5%～20%, Mg1.5%～4.5%, and RE0.01%～0.3%, all the other are Zn and unavoidable impurities;
B) its solvent is the aqueous solution, and chemical constitution is ZnCl
2200g/l～1000g/l, NH
4Cl 0g/l～200g/l, KCl 0g/l～100g/l, NaCl 0g/l～100g/l, rare earth chloride 0g/l～100g/l, the pH of solvent are 3～4;
C) temperature of plating bath is controlled at 450 ℃～580 ℃, and plating piece residence time in plating bath is 2s～300s.
2, the production method of the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion is good, employing be the technology of uncoiling-welding-(degreasing)-annealing-temperature adjustment-hot dip process-air knife wiping-cool off-batch, it is characterized in that,
A) Chemical Composition of its plating bath is Al2.5%～20%, Mg1.5%～4.5%, and RE0.01%～0.3%, all the other are Zn and unavoidable impurities;
B) temperature of being with steel to go into the zinc pot is 480 ℃～520 ℃, and the temperature of plating bath is controlled at 470 ℃～520 ℃, and plating piece residence time in plating bath is 2s～30s, and air knife pressure is 2kPa～80kPa, plating postcooling speed＞1 ℃/s.
3, the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion is good is characterized in that the chemical constitution of coating is by weight percentage: Al2.5%～20%, and Mg1.5%～4.5%, RE (mishmetal) 0.01%～0.2%, all the other are Zn and unavoidable impurities.
4, the production method of the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion according to claim 1 and 2 is good, the Chemical Composition that it is characterized in that its plating bath is Al2.5%～20%, Mg1.5%～4.5%, RE0.01%～0.3%, Si0.01%～0.5%, V0.0001%～0.2%, all the other are Zn and unavoidable impurities.
5, the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion according to claim 4 is good, it is characterized in that, the chemical constitution of coating is by weight percentage: Al2.5%～20%, Mg1.5%～4.5%, RE0.01%～0.2%, Si0.01%～0.5%, V0.0001%～0.2%, all the other are Zn and unavoidable impurities.
6, the production method of the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion according to claim 1 is good, the chemical constitution that it is characterized in that described solvent is ZnCl
2600～800g/l, NH
4Cl 0～200g/l, KCl 0～100g/l, NaCl 0～100g/l, rare earth chloride 0g/l～100g/l, the pH of solvent is controlled at 3～4.
7, the production method of the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion according to claim 1 is good is characterized in that shaped steel is carried out hot dip process, and its bath temperature is 450 ℃～560 ℃, and plating piece residence time in plating bath is 45s～300s.
8, the production method of the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion according to claim 1 is good is characterized in that steel wire is carried out hot dip process, and its bath temperature is 450 ℃～520 ℃, and plating piece residence time in plating bath is 10s～60s.
9, the production method of the zinc-aluminum-magnesium alloy layer steel that a kind of solidity to corrosion according to claim 1 is good is characterized in that steel plate, band steel are carried out hot dip process, and its bath temperature is 470 ℃～530 ℃, and plating piece residence time in plating bath is 2s～60s.
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| CNB2003101194449A CN100363526C (en) | 2003-12-22 | 2003-12-22 | Method for producing zinc-aluminum-magnesium alloy coated steel products with good corrosion resistance and zinc-aluminum-magnesium alloy coated steel products |
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|---|---|---|---|
| CNB2003101194449A CN100363526C (en) | 2003-12-22 | 2003-12-22 | Method for producing zinc-aluminum-magnesium alloy coated steel products with good corrosion resistance and zinc-aluminum-magnesium alloy coated steel products |
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|---|---|---|---|---|
| JP2002080952A (en) * | 2000-06-29 | 2002-03-22 | Nisshin Steel Co Ltd | Home building material excellent in corrosion resistance, and home building member |
| JP2002146504A (en) * | 2000-08-22 | 2002-05-22 | Nisshin Steel Co Ltd | Material for electrical equipment and member for electrical equipment having excellent corrosion resistance and whisker resistance |
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2003
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