CN102031541B - Method for producing zinc-magnesium coated steel sheet and zinc-magnesium coated steel sheet thereof - Google Patents
Method for producing zinc-magnesium coated steel sheet and zinc-magnesium coated steel sheet thereof Download PDFInfo
- Publication number
- CN102031541B CN102031541B CN 200910187779 CN200910187779A CN102031541B CN 102031541 B CN102031541 B CN 102031541B CN 200910187779 CN200910187779 CN 200910187779 CN 200910187779 A CN200910187779 A CN 200910187779A CN 102031541 B CN102031541 B CN 102031541B
- Authority
- CN
- China
- Prior art keywords
- zinc
- magnesium
- coated steel
- steel sheet
- magnesium coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a method for producing a zinc-magnesium coated steel sheet and the zinc-magnesium coated steel sheet thereof. The method is characterized in that: MgCl2, NaCl and alkyl heterocyclic halide or alkaryl ammonium halide are used as electroplate liquid, metal magnesium is used as an anode, and a galvanized steel sheet is used as a cathode for electroplating, and heating is performed; the coating has a structure with 2 to 3 layers; the surface layer consists of a MgZn2 phase and an eta(Zn) phase, and an eta(Zn) phase is arranged under the surface layer; and when hot dipped galvanized steel sheet is adopted, an inhibiting layer containing Fe2Al5Znx is arranged between the eta(Zn) phase and the steel sheet. The invention has the advantages that: magnesium is plated on the galvanized steel sheet to form a multi-layer structured coating through heat treatment, the surface layer contains the MgZn2 phase so the zinc-magnesium coated steel sheet has high corrosion resistance, and the eta(Zn) phase is arranged under the surface layer so the zinc-magnesium coated steel sheet has excellent toughness.
Description
Technical field
The invention belongs to field of electroplating, particularly a kind of production method of zinc-magnesium Coated Steel and zinc-magnesium Coated Steel thereof
Background technology
In zinc coating, add more than 1% the magnesium or in coating, form MgZn
2Can significantly improve mutually the solidity to corrosion of Coated Steel, this is had a large amount of bibliographical informations both at home and abroad.The adding of magnesium has changed the composition of corrosion product, and as in oceanic climate, the corrosion product of common galvanized sheet is zinc subcarbonate and basic zinc chloride; And behind the adding magnesium, the basic carbonate zinc-aluminium has replaced basic zinc chloride, forms simultaneously the magnesiumcarbonate of some amount, owing to the finer and close and water-soluble reduction of corrosion product, can increase substantially the erosion resistance of steel plate galvanized.
Yet, still do not have the economic good method that contains the magnesium steel plate galvanized of the higher while processing characteristics of solidity to corrosion that obtains at present.
Adopt hot dip coating method because the easy oxidation of magnesium causes the plating bath platability to descend, therefore be difficult to make the zinc-magnesium Coated Steel of high level, adopting the 5%Al0.01%Mg surplus such as II type GF is the method for Zn, because the few effect to the solidity to corrosion raising of magnesium add-on is limited, it is that Zn and 6%Al3%Mg surplus are Zn that Z11Al3MgSi and Z6Al3Mg adopt respectively the 11%Al3%Mg0.02%Si surplus, although Mg content is higher, the more common galvanized sheet of solidity to corrosion improves more than 4 times, and the Al that adds high level has improved the platability of plating bath, but because the existence of ZnAlMg ternary alloy and rich aluminium phase, ductility of electrodeposited film is relatively poor, is prone to crackle after the distortion.
JP8013186A discloses a kind of manufacture method of alloy Zn-Mg steel plate, adopts the method for Molten Salt Electroplating, and by control zinc/magnesium ion ratio and current density, the acquisition Mg content reaches the zinc-magnesium alloy coating steel plate more than 35%; JP4180592A discloses the manufacture method of the good zinc-magnesium alloy coating steel plate of a kind of sticking power and solidity to corrosion, adopts the method for Molten Salt Electroplating, and main salt is zinc chloride, magnesium chloride, and conducting salt is alkali metal chloride, current density 20～350A/dm
2, temperature is 350～500 ℃, thickness of coating is 10～60g/m
2(single face), Mg content is 1～35% in the coating of acquisition, and iron level is 0.5～25%, and surplus is zinc.These 2 kinds of method temperature of electroplating solution height are very large to equipment corrosion, and quality of coating also is difficult to guarantee.
JP2001234391A, US6607844B1, EP1036862A1 disclose a kind of zinc-magnesium electroplating steel plate and manufacture method thereof, contain 0.01～10% carbon, 0.08～40% magnesium in its coating, surplus is zinc, and its coating is to electroplate to obtain in the acidic aqueous solution that contains magnesium, zinc salt and tensio-active agent.The a large amount of liberations of hydrogen of this method electroplating process negative electrode, cathode efficiency is low, and magnesium is easily oxidation in plating bath, and coating adhesion is difficult to guarantee, is difficult to obtain the coating of higher Mg content.
Di Sen Iron And Steel Company adopts the method for physical vapor deposition (PVD), at electrogalvanizing steel plate surface deposition magnesium, forms zinc-magnesium alloy coating through thermal treatment again.The method needs higher vacuum tightness when physical vapor deposition, it is very large to process continuously band steel difficulty, and sedimentation velocity is very low, is difficult to be complementary with the Electro-galvanizing Production Line process speed.
Summary of the invention
The invention discloses a kind of corrosion resistance of coating and toughness are good, be easy to the zinc-magnesium Coated Steel of suitability for industrialized production production method and zinc-magnesium Coated Steel thereof, the problem that quality of coating is bad, plating process is difficult that exists to solve existing Coated Steel.
Process characteristic of the present invention is for adopting MgCl
2, NaCl and halogenated alkyl heterocycle or alkyl halide aryl ammonium salts solution be electroplate liquid, take MAGNESIUM METAL as anode, electroplates as negative electrode take steel plate galvanized, heat-treat after the plating.
Concrete technology is as follows, MgCl
2, NaCl and halogenated alkyl heterocycle or halogenation alkylaryl ammonium salts the ratio of mole number be 1～2: 0～1: 1;
The temperature of electroplate liquid is 10～60 ℃;
The speed of relative movement of steel plate and electrolytic solution is 20～300m/min;
Current density is 1～20A/dm
2, the thickness of electroplating the magnesium layer is 0.1～1 μ m;
Thermal treatment temp is 200～400 ℃, and the time is 2～60s.
Halogenated alkyl heterocycle described in the present invention is such as chlorination alkyl imidazoline, bromination alkyl pyridine etc.;
Described halogenation alkylaryl ammonium salts, such as chlorination alkyl benzene amine or chlorination alkyl benzyl amine etc., molecular weight is between 100～300.Molecular weight is lower than at 100 o'clock, and the solvent fusing point is low volatile, and molecular weight is higher than at 300 o'clock, and the solvent fusing point is too high, is difficult for and MgCl
2Form low melting point solution, be difficult to electroplate at normal temperature.
Steel plate galvanized of the present invention can be electrogalvanizing steel plate, also can be hot-dip galvanizing sheet steel.
The zinc-magnesium Coated Steel that adopts the inventive method to make has following characteristics,
Coating has 2～3-tier architecture, and the top layer is by MgZn
2Be η (Zn) phase below phase and η (Zn) phase composite, top layer, when adopting hot-dip galvanizing sheet steel, consist of in addition Fe mutually and between the steel plate at η (Zn)
2Al
5Zn
xThe inhibition layer.
MgCl in the technique of the present invention
2Be main salt, work as MgCl
2With the ratio of the mole number of solvent be 1～2: 1 o'clock, electroplate liquid has lower fusing point, it is acid that solution is, and can realize that magnesium is in the deposition of negative electrode.
NaCl is conducting salt and buffer reagent, and when the higher current density of needs, keep can suitably adding in the situation of solution long-term stability, but the ratio of the mole number of NaCl and solvent is greater than 1: 1 o'clock, and the sedimentation effect of Mg reduces.
When the temperature of electroplate liquid was lower than 10 ℃, current density was lower, and sedimentation velocity is low.The temperature of electroplate liquid is higher than 60 ℃, and the stability of solution reduces.
The speed of relative movement of steel plate and electrolytic solution is difficult to obtain higher current density less than 20m/min, and sedimentation effect is low.The speed of relative movement of steel plate and electrolytic solution is greater than 300m/min, and current density reaches capacity, and energy consumption increases.
Current density is less than 1A/dm
2, sedimentation velocity is excessively low, and it is low to make efficient.Current density is greater than 20A/dm
2, because a large amount of heat release is difficult to control bath temperature and guarantees quality of coating.
Electroplate the thickness of magnesium layer less than 0.1 μ m, limited to improving corrosion proof effect.Electroplate the thickness of magnesium layer greater than 1 μ m, electroplating time and heat treatment time increase, the thermal treatment difficulty of coating, and coating fragility increases.
When thermal treatment temp was lower than 200 ℃ or heat treatment time less than 2s, magnesium zinc can not spread mutually, can not reach to improve corrosion proof purpose.When heat treatment time surpasses 400 ℃, the easy oxidation of coating surface.When heat treatment time reached 60s, magnesium fully spread and forms MgZn
2Phase does not have necessity of further processing.
The invention provides a kind of industrialized zinc-magnesium Coated Steel production method and zinc-magnesium Coated Steel thereof of being easy to, its advantage and effect are to electroplate magnesium on the steel plate galvanized, form multilayered structure coating through thermal treatment, and MgZn is contained on the top layer
2Phase, solidity to corrosion is good, is η (Zn) phase below the top layer, and toughness is good.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated, adopt MgCl
2, NaCl and halogenated alkyl heterocycle or alkyl halide aryl ammonium salts solution be electroplate liquid, take MAGNESIUM METAL as anode, electroplates as negative electrode take steel plate galvanized, heat-treat after the plating.Its steel plate galvanized immerses in the electroplate liquid continuously, take MAGNESIUM METAL as anode, electroplates as negative electrode take steel plate galvanized, heat-treats after the plating.
The concrete technology parameter is as shown in table 1.
The zinc-magnesium Coated Steel that adopts the inventive method to produce, coating has 2～3-tier architecture, and the top layer is by MgZn
2Be η (Zn) phase below phase and η (Zn) phase composite, top layer, when adopting hot-dip galvanizing sheet steel, consist of in addition Fe mutually and between the steel plate at η (Zn)
2Al
5Zn
xThe inhibition layer.
Claims (4)
1. the production method of a zinc-magnesium Coated Steel is characterized in that, adopts MgCl
2, NaCl and halogenated alkyl heterocycle or alkyl halide aryl ammonium salts solution be electroplate liquid, take MAGNESIUM METAL as anode, electroplates as negative electrode take steel plate galvanized, heat-treat after the plating,
Concrete technology is as follows:
MgCl
2, NaCl and halogenated alkyl heterocycle or halogenation alkylaryl ammonium salts the ratio of mole number be 1～2:0～1:1;
The temperature of electroplate liquid is 10～60 ℃;
The speed of relative movement of steel plate and electrolytic solution is 20 ~ 300m/min;
Current density is 1～20A/dm
2
The thickness of electroplating the magnesium layer is 0.1 ~ 1 μ m;
Thermal treatment temp is 200～400 ℃, and the time is 2～60s;
Described halogenated alkyl heterocycle is specially chlorination alkyl imidazoline, bromination alkyl pyridine;
Described halogenation alkylaryl ammonium salts is specially chlorination alkyl benzene amine or chlorination alkyl benzyl amine, and molecular weight is between 100～300.
2. the production method of a kind of zinc-magnesium Coated Steel according to claim 1 is characterized in that, described steel plate galvanized is electrogalvanizing steel plate or hot-dip galvanizing sheet steel.
3. a zinc-magnesium Coated Steel that adopts the production method production of zinc-magnesium Coated Steel as claimed in claim 1 or 2 is characterized in that coating has 2～3-tier architecture, and the top layer is by MgZn
2Be η (Zn) phase below phase and η (Zn) phase composite, top layer.
4. the zinc-magnesium Coated Steel of the production method of a kind of zinc-magnesium Coated Steel according to claim 3 production when adopting hot-dip galvanizing sheet steel, consists of Fe mutually and between the steel plate at η (Zn)
2Al
5Zn
xThe inhibition layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910187779 CN102031541B (en) | 2009-09-30 | 2009-09-30 | Method for producing zinc-magnesium coated steel sheet and zinc-magnesium coated steel sheet thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910187779 CN102031541B (en) | 2009-09-30 | 2009-09-30 | Method for producing zinc-magnesium coated steel sheet and zinc-magnesium coated steel sheet thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102031541A CN102031541A (en) | 2011-04-27 |
| CN102031541B true CN102031541B (en) | 2013-03-13 |
Family
ID=43884967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910187779 Active CN102031541B (en) | 2009-09-30 | 2009-09-30 | Method for producing zinc-magnesium coated steel sheet and zinc-magnesium coated steel sheet thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102031541B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0424856A1 (en) * | 1989-10-23 | 1991-05-02 | Kawasaki Steel Corporation | Method of producing a steel sheet plated with Zn-Mg alloy superior both in plating adhesion and corrosion resistance, and sheet plated with the same |
-
2009
- 2009-09-30 CN CN 200910187779 patent/CN102031541B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0424856A1 (en) * | 1989-10-23 | 1991-05-02 | Kawasaki Steel Corporation | Method of producing a steel sheet plated with Zn-Mg alloy superior both in plating adhesion and corrosion resistance, and sheet plated with the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102031541A (en) | 2011-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2171130B1 (en) | Method of providing a metallic coating layer | |
| CN109234571B (en) | Tin-containing zinc-aluminum-magnesium coated steel plate with spangles and galvanizing method | |
| CN101922028B (en) | Galvanized iron (vanadium) alloy process of acid system | |
| CN108396198A (en) | No zinc spends rub resistance K-S-B allumens used for hot dip galvanizing and processing technology | |
| CN103981474A (en) | Highly anti-corrosion zinc-based alloy plating used for solvent method hot dipping of steel | |
| CN103695977A (en) | Electroplating method capable of enabling tin coating to be level and preventing tin whisker from growing | |
| CN105177659A (en) | Surface treatment process for improving corrosion resistance of copper foil | |
| CN102031541B (en) | Method for producing zinc-magnesium coated steel sheet and zinc-magnesium coated steel sheet thereof | |
| US4167459A (en) | Electroplating with Ni-Cu alloy | |
| CN101565843A (en) | Method for preparing zinc-magnesium alloy coating | |
| CN113529143A (en) | Leveling agent-containing ionic liquid aluminum plating liquid and aluminum plating process using same | |
| CN106514039A (en) | Copper-tin-titanium brazing filler metal and preparation method thereof | |
| JP2014234520A (en) | Method for producing electrogalvanized steel sheet | |
| JPH05214544A (en) | Highly corrosion-resistant galvanized steel sheet and its production | |
| CN102206840B (en) | Alkaline chloride copper-plating treatment agent and preparation method thereof | |
| CN108396196A (en) | Cold stamping spends Na-Er-Mo allumens used for hot dip galvanizing without zinc | |
| CN220450333U (en) | Plating layer structure of tin-plated cobalt alloy chromium substitution | |
| CN108441699A (en) | Fishery steel wire hot-dip allumen containing Mg and Ca under marine environment | |
| CN108330324A (en) | New zinc magnesium-based galvanizing by dipping spends Mg-In-Ni kirsites with no zinc | |
| CN108277387A (en) | Kirsite of the steel wire galvanizing by dipping containing Ru and Sn used under low temperature | |
| KR19990011059A (en) | A method of manufacturing a hot-dip galvanized steel sheet excellent in surface shape and corrosion resistance | |
| CN108396180A (en) | Energy-saving no white point and blackspot steel wire galvanizing by dipping kirsite containing Re | |
| CN108441695A (en) | A kind of face slag shape steel plate hot-dip aluminum zinc Ca-Al-Bi allumens | |
| JPS6367560B2 (en) | ||
| CN108396178A (en) | With the novel kirsite containing Cr of energy-conserving action steel wire galvanizing by dipping |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |