CN109023197A - A kind of preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection - Google Patents
A kind of preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection Download PDFInfo
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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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- 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
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- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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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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- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
- C25F1/06—Iron or steel
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Abstract
The present invention is a kind of preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.This method pre-processes hot-rolled mild steel sheet using mechanical derusting and electrolytic degreasing, is heated by HF induction heating apparatus to steel plate, in N2‑H2The steel plate pre-processed is restored to obtain the surface state of suitable hot-dip in mixed atmosphere.In N2Cooling metal sheets in atmosphere control immersion plating front spring temperature, the immersion plating in zinc-aluminum-magnesium alloy electroplating bath.Subsequent cooling metal sheets in air.Harm the invention avoids acid pickling and rust removing during conventional hot-dip and the polluter for helping plating process to generate to human body and environment, meets increasingly harsh environmental requirement, and improve quality of coating, has broad application prospects.
Description
Technical field
The present invention relates to Hot Galvanizing Technology field, in particular to the producer of the zinc-aluminium Mg Alloy Coating steel plate of a kind of environmental protection
Method.
Background technique
Steel material is yield maximum and the most wide metal material of purposes in the world, and with good toughness, intensity is high, hardness
Many advantages, such as height, production economy is high.However, in use, steel material is chronically exposed to humid air and seawater
In, or often under the complex working conditions such as strong corrosive, industrial high temperature, therefore it is easy to happen corrosion phenomenon.Anodic protection, yin
Pole protection, adds inhibitor, protective coating and metal coating are all common means of defences.Spelter coating is widely used in the guarantor of steel
Shield.In this case, reactive zinc metal prevents steel from generating anodic attack by cathode reaction corrosion more preferential than steel substrate.
Different types of spelter coating includes: galvanizing by dipping (batch or continuous), and plating is metallized (zinc spraying), mechanical plating and zinc-rich
Coating.Wherein, hot dip galvanizing process provides high intensity, and mouldability is excellent, light-weight, good corrosion resistance, inexpensive and recyclable
The unique combination of the good characteristics such as property.
For hot galvanizing, different industries have different needs.Such as automobile industry needs light weight and great surface quality
Zinc layers, household electric appliances need to shield the zinc layers of electromagnetic noise and heat radiation, and building trade needs corrosion resistant zinc layers.Different
The exploitation for needing to have promoted variety classes zinc layers, in addition to traditional galvanized steel plain sheet (Zn-0.2%Al), other products have
Galvannealed (Zn-~10%Fe), galvalume (55%Al-43.5%Zn-1.5%Si) and galfan (Zn-5%
Al) etc..Al and Mg is added into zinc liquid can be further improved alloy corrosion resistance energy, and Japanese scientific research personnel develops different
Zinc-aluminum-magnesium alloy system, such as ZAM (Zn-6%Al-3%Mg), DymaZinc (Zn-0.5%Mg), SuperDyma (Zn-11%
) etc. Al-3%Mg-0.2%Si it is used widely in Japan.
Due to the lag of basic theory and application aspect, home products in terms of quality with international most advanced level it
Between there is very big gap, the country relies primarily on import, and expensive, even if haveing excellent performance for zinc-aluminum-magnesium coating, does not have yet
Wide popularization and application can be obtained by having.
Hot dip galvanizing process is broadly divided into solvent method and reduction method, and solvent method is conventional hot-dip method, process flow letter
Single, low to workpiece requirement, loss of strength is small, but uses solvent method hot-dip aluminum zinc magnesium alloy to exist and pollute big, energy consumption height, plating
A series of problems, such as layer unstable quality, and reduction method hot-dip aluminum zinc magnesium alloy compared to solvent method have production closing, it is continuous,
It is the features such as efficient, relatively preferable to quality of coating control, there is the very high market advantage, but it is very high to technique requirement, only exist
It is used widely in a few countries such as Japan, market prospects are very big.
It is more for the research of zinc-aluminium magnesium alloy at present, but be to the heterogeneous microstructure of zinc-aluminium magnesium alloy and its resistance to mostly
Corrosive basic discussion, influence of few research reduction method techniques to hot-dip aluminum zinc magnesium alloy, therefore study reduction method
Dip galvanized aluminum magnesium alloying technology formulates the reasonable technological parameter of high-efficiency environment friendly, and the quality for improving alloy layer has important reason
By with practice significance.
CN104711502A " a kind of anti-corrosion zinc-aluminium magnesium-rare earth alloy coating and its preparation and hot dip coating method " is disclosed
Steel plate is the ZnCl2 that concentration is 250~280g/L through alkali cleaning, pickling, washing, fluxing agent ingredient, and concentration is 40~60g/L's
NH4Cl, concentration are the AlCl3 of 40~60g/L, and concentration is the LiCl of 30~50g/L, and concentration is the emulsifier op-10 of 4~8g/L
And after helping plating 1-2min in the solution of aqueous solvent, at 600~620 DEG C, ingredient is that Al content is 3~9wt%, and Mg content is
0.03~0.09wt%, content of rare earth are 0.01~0.15wt%, and surplus is 10~20s of immersion plating in the plating solution of zinc, are obtained anti-corrosion
Zinc-aluminium magnesium-rare earth alloy coating.
CN1632157A " the good zinc-aluminum-magnesium alloy coated steel production method of corrosion resistance and zinc-aluminum-magnesium alloy coated steel "
Disclose technique dip galvanized aluminum magnesium of the steel plate through degreasing~washing~pickling~painting solvent~drying~hot-dip~air-cooled
Alloy.Wherein solvent is aqueous solution, and chemical composition is the ZnCl2 that concentration is 200~1000g/L, and concentration is 0~200g/L's
NH4Cl, concentration are the KCl of 0~100g/L, and concentration is the NaCl of 0~100g/L, and concentration is the rare earth chloride of 0~100g/L, molten
The pH of agent is 3~4.At 450~580 DEG C, ingredient is that Al content is 2.5~20wt%, and Mg content is 1.5~4.5wt%, rare earth
Content is 0.01~0.3wt%, and surplus is 2~300s of immersion plating in the plating solution of zinc, obtains the good zinc-aluminium Mg Alloy Coating of corrosion resistance.
The above patent is all made of solvent method in dip galvanized aluminum magnesium alloy process, i.e., carries out pickling to steel plate before hot dip
Plating is derusted and helped, the harmful substances such as spent acid can be generated during processing, caused damages to human body and environment.Therefore, it looks for
To a kind of process of hot-dip aluminum zinc magnesium alloy that environment-friendly high-efficiency is stable, and high quality alloy layer can be obtained, meeting can
Sustainable development and requirement to environmental protection.
Summary of the invention
It is an object of the invention to provide a kind of zinc-aluminium Mg Alloy Coating of environmental protection for deficiency present in current techniques
The preparation method of steel plate.This method is in mechanical derusting, electrolytic degreasing, N2-H2Mixed atmosphere restore steel plate and etc. on, by skilful
Wonderful production order and relevant parameter, realize has the pickling of pollution and fluxing agent to help plating process instead of traditional.Energy of the present invention
Enough to avoid generating to the polluters such as human body and the harmful spent acid exhaust gas of environment in process of production, it is smooth to obtain any surface finish,
Defect is few, the good alloy layer with steel plate binding force.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection, includes the following steps:
(1) alloy molten: for one of following two method:
Method one: according to Al:6wt%, Mg:3wt%, surplus is that the proportion of Zn takes zinc ingot metal, magnesium ingot, aluminium ingot and aluminium foil；It will
Zinc is heated to 500 DEG C~550 DEG C and is completely melt, then sequentially adds aluminium block into zinc liquid to melting, adds use after stirring
The MAG block that aluminium foil wraps, until fusing；Aluminium alloy is warming up to 560 DEG C~600 DEG C again, every 30min stirring is primary, heat preservation 5~
10h, for use；
Alternatively, method two: by ZAM alloy melting, then to 560 DEG C~600 DEG C, every 30min stirring is primary, heat preservation 5~
10h, for use；
(2) polishing derusting mechanical derusting: is carried out to hot rolled steel plate using continuous rust remover；
(3) electrolytic degreasing: preparing the NaOH solution that mass fraction is 5~10wt%, and solution temperature is 40~80 DEG C, uses
D.C. regulated power supply output voltage electric current, steel plate to be cleaned of cylinder is as cathode, and as anode material, adjust current density is graphite
3A/dm2~6A/dm2,5~20min of scavenging period are washed after cleaning, drying；
(4) steel plate restores: steel plate is placed in N2-H2In mixed atmosphere, wherein H2Content is 1vol%~40vol%, is passed through
Steel plate is heated to 800~850 DEG C by HF induction heating apparatus, is restored in atmosphere；High-frequency induction heating frequency is
220kHz, heating power are 1.4~1.7kW, and the recovery time in atmosphere is 10~60s；
(5) adjustment plating front spring temperature: by the steel plate after reduction in N2Cool down in atmosphere, make steel billet temperature be reduced to 400~
700℃；
(6) hot-dip aluminum zinc magnesium alloy: the steel plate that upper step obtains is immersed into the aluminium alloy in (1) step, when immersion plating
Between 5~60s, bath temperature be 380~550 DEG C, it is air-cooled after plating, finally obtain environmental protection zinc-aluminium Mg Alloy Coating steel plate.
The hot rolled steel plate is preferably Q235 steel plate.
The invention has the benefit that
Current hot dip be largely using acid pickling and rust removing, in other methods, not only complex process, the high requirements on the equipment, and
Requirement to steel plate is also very harsh.The present invention uses mechanical derusting, electrolytic degreasing, N2-H2Mixed atmosphere reduction steel plate and etc.,
There are the pickling of pollution and fluxing agent to help plating process instead of traditional, avoids pollution caused by the generation of spent acid exhaust gas, reduce
It is endangered caused by human body and environment in production process, and the quality of coating obtained after hot-dip is good, such as Fig. 1 embodiment 3
Shown, coating surface is smooth, no plating leakage, without obvious list edge.Coating microstructure even compact, in conjunction with steel matrix preferably, such as Fig. 3 reality
It applies shown in example 3, coating sectional uniform is straight, tissue stabilization, ensure that coating in conjunction with matrix stable.
Detailed description of the invention
Fig. 1 is the photomacrograph of hot-dip aluminum zinc Mg Alloy Coating in the embodiment of the present invention 3.
Fig. 2 is the surface XRD spectrum of hot-dip aluminum zinc Mg Alloy Coating in the embodiment of the present invention 3.
Fig. 3 is the section SEM picture of hot-dip aluminum zinc Mg Alloy Coating in the embodiment of the present invention 3.
Fig. 4 is the section SEM picture of hot-dip aluminum zinc Mg Alloy Coating in the embodiment of the present invention 5.
Specific embodiment
With reference to the accompanying drawings of the specification with specific embodiment to a kind of zinc-aluminium Mg Alloy Coating of environmental protection of the present invention
The preparation method of steel plate is further described.
ZAM zinc-magnesium aluminium alloy of the present invention is well known materials, commercially available to obtain or by being prepared.
The purity of zinc ingot metal of the present invention, magnesium ingot, aluminium ingot and aluminium foil is respectively 99.97%, 99.94%, 99.65%,
99.72%.
Embodiment 1
The preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
According to Al:6wt%, Mg:3wt%, surplus is that the proportion of Zn takes zinc ingot metal, magnesium ingot, aluminium ingot and the aluminium foil (quality of aluminium foil
It is included in the content of aluminium).Zinc is heated to 500 DEG C to be completely melt, has weighed aluminium block, aluminium block is pressed into galvanizing zinc with graphite rod
In to being completely melt, and stir.MAG block has been weighed, has been wrapped with aluminium foil, has been pressed into galvanizing zinc with graphite rod to completely molten
Change, to reduce oxidation ablation loss.Aluminium alloy is warming up to 560 DEG C, every 30min stirring is primary, keeps the temperature 5h, for use.
Mechanical derusting: use continuous rust remover to hot rolling Q235 steel plate (the specific material of Q235 steel plate for C:0.12~
0.2wt%, Mn:0.3~0.65wt%, Si:0.17~0.3wt%, S :≤0.045wt%, P :≤0.035wt%, Cr :≤
0.25wt%, Ni :≤0.25wt%, surplus Fe.Following embodiment is same) polishing derusting is carried out, to clear up surface of steel plate corrosion,
Improve sequential reduction, hot-dip production efficiency.
Electrolytic degreasing is carried out to the Q235 steel plate after mechanical derusting, prepares the NaOH solution of 5wt%, solution temperature 60
DEG C, using the D.C. regulated power supply output voltage electric current of model WYJ-0~15V5A.Steel plate to be cleaned of cylinder is made as cathode, graphite
For anode material, adjusting current density is 3A/dm2, scavenging period 5min, then washes, dries.
Steel plate is heated to 800 DEG C by the HF induction heating apparatus of model SPG-06A- II, is carried out in atmosphere
Reduction.High-frequency induction heating frequency is 220kHz, heating power 1.4kW.Reducing atmosphere is 0.1vol%H2-N2, the recovery time
40s；By the steel plate after reduction in N2It is cooling in atmosphere, changed by infrared radiation thermometer real-time detection steel billet temperature, makes hot-dip
Front spring temperature is 400 DEG C, sets 380 DEG C of bath temperature, steel plate obtained above is immersed into alloy electroplating bath, the immersion plating time
5s, it is air-cooled after plating, finally obtain the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
Coating surface is smooth, there is a small amount of plating leakage, and after bend test is tested, coating has a small amount of peeling, coating and steel plate knot
It closes poor.Illustrate H in atmosphere2Content is low, cannot effectively restore the residual oxide of Q235 surface of steel plate, lead to coating and steel plate
In conjunction with poor, and there is a small amount of plating leakage.
Embodiment 2
The preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
According to Al:6wt%, Mg:3wt%, surplus is that the proportion of Zn takes zinc ingot metal, magnesium ingot, aluminium ingot and aluminium foil.Zinc is heated to
520 DEG C are completely melt, have weighed aluminium block, and aluminium block is pressed into galvanizing zinc to being completely melt with graphite rod, and stirs.It weighs
MAG block is wrapped with aluminium foil, is pressed into galvanizing zinc with graphite rod to being completely melt, to reduce oxidation ablation loss.It will close
Golden liquid is warming up to 580 DEG C, and every 30min stirring is primary, keeps the temperature 8h, for use.
Mechanical derusting: carrying out polishing derusting to hot rolling Q235 steel plate using continuous rust remover, to clear up surface of steel plate corrosion,
Improve sequential reduction, hot-dip production efficiency.
Electrolytic degreasing is carried out to the Q235 steel plate after mechanical derusting, prepares the NaOH solution of 5wt%, solution temperature 40
DEG C, using the D.C. regulated power supply output voltage electric current of model WYJ-0~15V5A.Steel plate to be cleaned of cylinder is made as cathode, graphite
For anode material, adjusting current density is 3A/dm2, scavenging period 10min, then washes, dries.
Steel plate is heated to 830 DEG C by the HF induction heating apparatus of model SPG-06A- II, is carried out in atmosphere
Reduction.High-frequency induction heating frequency is 220kHz, heating power 1.5kW.Reducing atmosphere is 10vol%H2-N2, the recovery time
20s, by the steel plate after reduction in N2It is cooling in atmosphere, changed by infrared radiation thermometer real-time detection steel billet temperature, makes hot-dip
Front spring temperature is 500 DEG C, sets 460 DEG C of bath temperature, steel plate obtained above is immersed into alloy electroplating bath, the immersion plating time
60s, it is air-cooled after plating, finally obtain the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
Coating surface is smooth, and no plating leakage has a small amount of list edge, and after bend test is tested, coating is peeled off without obvious, coating with
Steel plate is combined.
Embodiment 3
The preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
According to Al:6wt%, Mg:3wt%, surplus is that the proportion of Zn takes zinc ingot metal, magnesium ingot, aluminium ingot and aluminium foil.Zinc is heated to
520 DEG C are completely melt, have weighed aluminium block, and aluminium block is pressed into galvanizing zinc to being completely melt with graphite rod, and stirs.It weighs
MAG block is wrapped with aluminium foil, is pressed into galvanizing zinc with graphite rod to being completely melt, to reduce oxidation ablation loss.It will close
Golden liquid is warming up to 560 DEG C, and every 30min stirring is primary, keeps the temperature 5h, for use.
Mechanical derusting: carrying out polishing derusting to hot rolling Q235 steel plate using continuous rust remover, to clear up surface of steel plate corrosion,
Improve sequential reduction, hot-dip production efficiency.
Electrolytic degreasing is carried out to the Q235 steel plate after mechanical derusting, prepares the NaOH solution of 8wt%, solution temperature 80
DEG C, using the D.C. regulated power supply output voltage electric current of model WYJ-0~15V5A.Steel plate to be cleaned of cylinder is made as cathode, graphite
For anode material, adjusting current density is 5A/dm2, scavenging period 5min, then washes, dries.
Steel plate is heated to 840 DEG C by the HF induction heating apparatus of model SPG-06A- II, is carried out in atmosphere
Reduction.High-frequency induction heating frequency is 220kHz, heating power 1.5kW.Reducing atmosphere is 10vol%H2-N2, the recovery time
40s, by the steel plate after reduction in N2It is cooling in atmosphere, changed by infrared radiation thermometer real-time detection steel billet temperature, makes hot-dip
Front spring temperature is 600 DEG C, sets 460 DEG C of bath temperature, steel plate obtained above is immersed into alloy electroplating bath, the immersion plating time
40s, it is air-cooled after plating, finally obtain the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
Fig. 1 is the macro morphology figure of 3 hot dip galvanizing -6wt%Al-3wt%Mg alloy layer of embodiment, three groups of coating in figure
Sample is coating obtained by the three repeated experiments that carry out under the conditions of embodiment 3.Three groups of coating surfaces are smooth bright and clean, and surface is without leakage
Plating, coating lower part are caused by gathering during zinc liquid stream is dynamic, not influence actual production use.Without obvious list edge, pass through
CMT6104 type electronic universal tester carries out bend test test to three groups of clad steel sheets, and coating is peeled off without obvious, coating and steel
It is hardened to get togather.
Fig. 2 is the XRD spectrum on 3 hot dip galvanizing -6wt%Al-3wt%Mg alloy layer surface of embodiment, by map it is found that
Coating surface is by Zn, Al, MgZn2Three phase compositions, the tiny MgZn of coating surface2There is important shadow to the corrosion resistance for improving coating
It rings.
Fig. 3 is 3 hot dip galvanizing -6wt%Al-3wt%Mg alloy layer cross-sectional scans picture of embodiment, as seen from the figure
Coating solidification layer is by Zn-MgZn2Binary eutectic tissue composition, the streaky structure at matrix are Fe2Al5Alloy-layer, coating with
Matrix combines fine and close.
Embodiment 4
The preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
According to Al:6wt%, Mg:3wt%, surplus is that the proportion of Zn takes zinc ingot metal, magnesium ingot, aluminium ingot and aluminium foil.Zinc is heated to
530 DEG C are completely melt, have weighed aluminium block, and aluminium block is pressed into galvanizing zinc to being completely melt with graphite rod, and stirs.It weighs
MAG block is wrapped with aluminium foil, is pressed into galvanizing zinc with graphite rod to being completely melt, to reduce oxidation ablation loss.It will close
Golden liquid is warming up to 580 DEG C, and every 30min stirring is primary, keeps the temperature 10h, for use.
Mechanical derusting: carrying out polishing derusting to hot rolling Q235 steel plate using continuous rust remover, to clear up surface of steel plate corrosion,
Improve sequential reduction, hot-dip production efficiency.
Electrolytic degreasing is carried out to the Q235 steel plate after mechanical derusting, prepares the NaOH solution of 8wt%, solution temperature 40
DEG C, using the D.C. regulated power supply output voltage electric current of model WYJ-0~15V5A.Steel plate to be cleaned of cylinder is made as cathode, graphite
For anode material, adjusting current density is 6A/dm2, scavenging period 20min, then washes, dries.
Steel plate is heated to 850 DEG C by the HF induction heating apparatus of model SPG-06A- II, is carried out in atmosphere
Reduction.High-frequency induction heating frequency is 220kHz, heating power 1.7kW.Reducing atmosphere is 20vol%H2-N2, the recovery time
60s, by the steel plate after reduction in N2It is cooling in atmosphere, changed by infrared radiation thermometer real-time detection steel billet temperature, makes hot-dip
Front spring temperature is 600 DEG C, sets 550 DEG C of bath temperature, steel plate obtained above is immersed into alloy electroplating bath, the immersion plating time
10s, it is air-cooled after plating, finally obtain the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
Coating surface is smooth, no plating leakage, and without obvious list edge, after bend test is tested, coating is peeled off without obvious, coating with
Steel plate is combined.
Embodiment 5
The preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
According to Al:6wt%, Mg:3wt%, surplus is that the proportion of Zn takes zinc ingot metal, magnesium ingot, aluminium ingot and aluminium foil.Zinc is heated to
550 DEG C are completely melt, have weighed aluminium block, and aluminium block is pressed into galvanizing zinc to being completely melt with graphite rod, and stirs.It weighs
MAG block is wrapped with aluminium foil, is pressed into galvanizing zinc with graphite rod to being completely melt, to reduce oxidation ablation loss.It will close
Golden liquid is warming up to 600 DEG C, and every 30min stirring is primary, keeps the temperature 8h, for use.
Mechanical derusting: carrying out polishing derusting to hot rolling Q235 steel plate using continuous rust remover, to clear up surface of steel plate corrosion,
Improve sequential reduction, hot-dip production efficiency.
Electrolytic degreasing is carried out to the Q235 steel plate after mechanical derusting, prepares the NaOH solution of 10wt%, solution temperature 60
DEG C, using the D.C. regulated power supply output voltage electric current of model WYJ-0~15V5A.Steel plate to be cleaned of cylinder is made as cathode, graphite
For anode material, adjusting current density is 5A/dm2, scavenging period 10min, then washes, dries.
Steel plate is heated to 820 DEG C by the HF induction heating apparatus of model SPG-06A- II, is carried out in atmosphere
Reduction.High-frequency induction heating frequency is 220kHz, heating power 1.4kW.Reducing atmosphere is 40vol%H2-N2, the recovery time
10s, by the steel plate after reduction in N2It is cooling in atmosphere, changed by infrared radiation thermometer real-time detection steel billet temperature, makes hot-dip
Front spring temperature is 750 DEG C, sets 580 DEG C of bath temperature, steel plate obtained above is immersed into alloy electroplating bath, the immersion plating time
10s, it is air-cooled after plating, finally obtain the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.Coating surface has more list edge, through curved without plating leakage
After bent experimental test, coating has a small amount of peeling, and coating is poor in conjunction with steel plate.
Fig. 4 is 5 hot dip galvanizing -6wt%Al-3wt%Mg alloy layer cross-sectional scans picture of embodiment, as seen from the figure
Thickness of coating increases, Fe at nearly matrix in coating2Al5Alloy layer thickness increases, and many holes occurs, this is because before immersion plating
Steel billet temperature and zinc liquid temperature are relatively high, lead to Fe, and Al reaction acutely, produces thicker and unstable alloy-layer, causes to plate
Layer declines with steel plate binding force.
By above embodiments it will be seen that
(1) surface of steel plate can remove most of corrosion and oxide skin through mechanical derusting, but inevitable after derusting
The defects of ground still has the oxide of a certain amount of iron to remain, and be easy to cause plating leakage, list edge, it is therefore desirable to hydrogen reducing is used, it will
The oxide of iron is reduced into the sponge iron of porosity and looseness, is conducive to plating solution and steel matrix combines.As H in reducing atmosphere2Content is low
When 0.1vol%, reduction is insufficient, and interface causes binding force of cladding material to decline there are still the oxide of iron, works as reducing atmosphere
Middle H2When content is higher than 40vol%, the production cost increases.
(2) contain Al:6wt% in alloy electroplating bath of the present invention, the addition of Mg:3wt%, aluminium element can inhibit
Brittle fe-zn alloy layer generates, and generates ferroalloy parts, improves the binding force of coating, the addition of magnesium elements can refine
Coating microstructure, hence it is evident that the corrosion resistance for improving coating makes coating have trimming protective value, formed in coating surface tiny
MgZn2Tissue improves the anti-grinded hardness index of corrosion resistance and coating.When content of magnesium is more than 3wt%, corrosion resistance of coating improves unknown
It is aobvious, and cadmia increases in plating solution.
(3) one of an important factor for plating front spring temperature is influence quality of coating, plating front spring temperature is excessively high, aluminium in plating solution
Acutely with the iron reaction in steel plate, cause surface list edge more, quality of coating is poor.It is too low to plate front spring temperature, then plating solution heat loss
Seriously, bath temperature is unstable, causes quality of coating unstable, is easy to appear plating leakage.
(4) immersion plating time and bath temperature also have a major impact coating.In order to obtain ideal quality of coating, when immersion plating
Between should control in 5~60s, bath temperature is 380~550 DEG C.The immersion plating time is too short, and plating solution and steel plate reaction are uneven, cannot
Metallurgical bonding is formed, plating leakage is easy to produce.Immersion plating overlong time, iron aluminium overreaction, causes ferroalloy parts blocked up, influences to plate
Layer binding force and corrosion resistance.Bath temperature is too low, then flow of the electrolyte is poor, influences the surface quality of coating.Bath temperature is excessively high,
Steel plate iron loss increases, and cadmia increases in plating solution, big to equipment loss, increases production cost.
Unaccomplished matter of the present invention is well-known technique.
Claims (2)
1. the preparation method of the zinc-aluminium Mg Alloy Coating steel plate of a kind of environmental protection, it is characterized in that including the following steps:
(1) alloy molten: for one of following two method:
Method one: according to Al:6wt%, Mg:3wt%, surplus is that the proportion of Zn takes zinc ingot metal, magnesium ingot, aluminium ingot and aluminium foil；Zinc is heated
It is completely melt to 500 DEG C ~ 550 DEG C, then sequentially adds aluminium block into zinc liquid to melting, add after stirring and wrapped up with aluminium foil
Good MAG block, until fusing；Aluminium alloy is warming up to 560 DEG C ~ 600 DEG C again, every 30min stirring is primary, keeps the temperature 5 ~ 10h, for use；
Alternatively, method two: by ZAM alloy melting, then to 560 DEG C ~ 600 DEG C, every 30min stirring is primary, keeps the temperature 5 ~ 10h, to
With；
(2) polishing derusting mechanical derusting: is carried out to hot rolled steel plate using continuous rust remover；
(3) electrolytic degreasing: the NaOH solution that mass fraction is 5 ~ 10wt% is prepared, solution temperature is 40 ~ 80 DEG C, steady using direct current
Voltage source output voltage electric current, steel plate to be cleaned of cylinder as cathode, graphite as anode material, adjusting current density be 3A/dm2 ~
6A/dm2,5 ~ 20min of scavenging period are washed after cleaning, drying；
(4) steel plate restores: steel plate is placed in N2-H2In mixed atmosphere, wherein H2Content is 1vol% ~ 40vol%, passes through high frequency sense
It answers heating equipment that steel plate is heated to 800 ~ 850 DEG C, is restored in atmosphere；High-frequency induction heating frequency is 220kHz, is added
Thermal power is 1.4 ~ 1.7kW, and the recovery time in atmosphere is 10 ~ 60s；
(5) adjustment plating front spring temperature: by the steel plate after reduction in N2Cool down in atmosphere, steel billet temperature is made to be reduced to 400 ~ 700 DEG C；
(6) hot-dip aluminum zinc magnesium alloy: the steel plate that upper step obtains is immersed into the aluminium alloy in (1) step, and the immersion plating time 5 ~
60s, bath temperature is 380 ~ 550 DEG C, air-cooled after plating, finally obtains the zinc-aluminium Mg Alloy Coating steel plate of environmental protection.
2. the preparation method of the zinc-aluminium Mg Alloy Coating steel plate of environmental protection as described in claim 1, it is characterized in that the hot rolling
Steel plate is Q235 steel plate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680685A (en) * | 2020-12-17 | 2021-04-20 | 新冶高科技集团有限公司 | Production method of high corrosion-resistant coating steel bar |
| CN114107860A (en) * | 2021-10-19 | 2022-03-01 | 上海大学 | Zinc-aluminum-magnesium-based alloy coating material for inhibiting liquid metal from being embrittled and improving wear resistance in hot forming process of high-strength steel and preparation method thereof |
| CN114351072A (en) * | 2021-12-29 | 2022-04-15 | 北华航天工业学院 | Production process of alloyed coated steel bar |
| CN116356240A (en) * | 2023-04-11 | 2023-06-30 | 湘潭大学 | Preparation method of low-aluminum zinc-aluminum-magnesium alloy coating |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422041A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | Ti-contained ZAM hot-dip galvanized zinc alloy and preparation method thereof |
| CN104711502A (en) * | 2013-12-15 | 2015-06-17 | 河南省电力勘测设计院 | Corrosion-resistant Zn-Al-Mg rare earth alloy coating, preparation and hot dipping method thereof |
| CN106756562A (en) * | 2017-01-09 | 2017-05-31 | 天津海钢板材有限公司 | A kind of high strength galvanized steel plate and its production technology |
| CN108265252A (en) * | 2018-01-19 | 2018-07-10 | 河北工业大学 | A kind of environmental protection hot-dipping method |
| CN108486415A (en) * | 2018-04-23 | 2018-09-04 | 马钢(集团)控股有限公司 | A kind of preparation method of steel plate and steel plate after dip galvanized aluminum magnesium plating solution and its hot-dip |
| CN108588491A (en) * | 2018-06-05 | 2018-09-28 | 马鞍山钢铁股份有限公司 | A kind of hot dip galvanizing-Al-Mg clad steel sheets that immersion plating is excellent and production method |
-
2018
- 2018-10-15 CN CN201811196154.7A patent/CN109023197B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103422041A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | Ti-contained ZAM hot-dip galvanized zinc alloy and preparation method thereof |
| CN104711502A (en) * | 2013-12-15 | 2015-06-17 | 河南省电力勘测设计院 | Corrosion-resistant Zn-Al-Mg rare earth alloy coating, preparation and hot dipping method thereof |
| CN106756562A (en) * | 2017-01-09 | 2017-05-31 | 天津海钢板材有限公司 | A kind of high strength galvanized steel plate and its production technology |
| CN108265252A (en) * | 2018-01-19 | 2018-07-10 | 河北工业大学 | A kind of environmental protection hot-dipping method |
| CN108486415A (en) * | 2018-04-23 | 2018-09-04 | 马钢(集团)控股有限公司 | A kind of preparation method of steel plate and steel plate after dip galvanized aluminum magnesium plating solution and its hot-dip |
| CN108588491A (en) * | 2018-06-05 | 2018-09-28 | 马鞍山钢铁股份有限公司 | A kind of hot dip galvanizing-Al-Mg clad steel sheets that immersion plating is excellent and production method |
Non-Patent Citations (2)
| Title |
|---|
| 胡国辉主编: "《金属磷化工艺技术》", 31 January 2009, 国防工业出版社 * |
| 马瑞娜等: ""冷却速度对Zn-Al-Mg合金组织及腐蚀性能的影响"", 《材料热处理学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680685A (en) * | 2020-12-17 | 2021-04-20 | 新冶高科技集团有限公司 | Production method of high corrosion-resistant coating steel bar |
| CN114107860A (en) * | 2021-10-19 | 2022-03-01 | 上海大学 | Zinc-aluminum-magnesium-based alloy coating material for inhibiting liquid metal from being embrittled and improving wear resistance in hot forming process of high-strength steel and preparation method thereof |
| CN114351072A (en) * | 2021-12-29 | 2022-04-15 | 北华航天工业学院 | Production process of alloyed coated steel bar |
| CN114351072B (en) * | 2021-12-29 | 2024-03-05 | 北华航天工业学院 | Production process of alloyed plated steel bar |
| CN116356240A (en) * | 2023-04-11 | 2023-06-30 | 湘潭大学 | Preparation method of low-aluminum zinc-aluminum-magnesium alloy coating |
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