CN107177809A - A kind of galvanizing by dipping kalzium metal coating and its hot dip coating method - Google Patents
A kind of galvanizing by dipping kalzium metal coating and its hot dip coating method Download PDFInfo
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- CN107177809A CN107177809A CN201710541261.8A CN201710541261A CN107177809A CN 107177809 A CN107177809 A CN 107177809A CN 201710541261 A CN201710541261 A CN 201710541261A CN 107177809 A CN107177809 A CN 107177809A
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- aluminium
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- galvanizing
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- zinc
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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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention provides a kind of galvanizing by dipping kalzium metal coating, the composition containing following percentage composition：Aluminium 4% 6.5%, calcium 0.1 0.8%, surplus is zinc and inevitable impurity；The impurity includes lead, cadmium, tin, antimony, total amount≤0.05%；The aluminium, calcium are added with zinc-aluminium intermediate alloy and aluminium calcium intermediate alloy mode；The hot-dip temperature of the galvanizing by dipping kalzium metal coating is 430 DEG C 450 DEG C；Time is 10s 3min.The galvanizing by dipping kalzium metal coating of the present invention is cheap, can batch hot-dip, hot plating technology be simple, good corrosion resistance, better than Zn 5%Al RE；In terms of steel anti-corrosion, especially there is broad prospect of application in heavy corrosion area.
Description
Technical field
The invention belongs to anti-corrosion of metal field, and in particular to Zn-Al-Ca alloy layers and its hot dip coating method.
Background technology
Galvanizing by dipping is a kind of effective steel surface anticorrosion process.Zinc coat has buffer action to steel substrate material
With cathodic protection effect, in most of natural environments, the corrosion rate of zinc only has the 1/10-1/100 of steel, therefore can be to steel
Matrix provides preferable protective effect.
In industrial pollution, coastal and moist etc. area, the anti-corrosion life of conventional hot-dip zinc layers is substantially reduced, tended not to
Meet design requirement.Research is found in zinc-plated middle addition aluminium, can improve the corrosion resisting property of coating, with the increase of Al content, plating
The corrosion resistance of layer is improved, when reaching Zn-Al eutectic compositions (Al content 5% or so), and coating is mainly alternately divided by flake
α-Al the phases of cloth and β-Zn phase compositions.In addition, the alloy of eutectic composition also has relatively low fusing point, hot-dip is adapted for.
The Zn-5%Al-RE of Ce-La mixed rare earth formation is added on the basis of this（Business name Galfan）, corrosion resistance is the 2-3 of hot pure zinc plating
Times.
Zinc-aluminium Mg Alloy Coating has more preferable corrosion resisting property, such as Zn-6%Al-3%Mg alloy layers, as grinding in recent years
The focus studied carefully.But when Mg is added in zn-al alloy coating metal, the manufacturability of batch hot-dip is deteriorated, coating is coarse, and production
Raw plating leakage, due to not applicable fluxing agent, cannot be used for batch hot-dip, is only applied to continuous hot-dipping technique at present, use
In the thin plate as washing machine shell, automobile case, it is impossible to be used in large-scale steel structure.Currently due to air pollution, air is rotten
Corrosion is aggravated, very strong to improving the hot-dip coated corrosion proof demand of batch.Therefore, what research was new can batch hot-dip, valency
Lattice are cheap, can replace rare earth and have the alloy layer of more preferable rotproofness significant.
The content of the invention
It is an object of the invention to provide a kind of Novel hot immersion plating Zn-Al-Ca alloy layers, with Galfan alloy coating (Zn-
5%Al-RE) compare, the alloy layer has more preferable corrosion resisting property, Ca elements rich content in the earth's crust can replace rare money
Source rare earth element.
It is a further object of the present invention to provide a kind of batch hot dip coating method of above-mentioned alloy layer.
To achieve the above object, the present invention is adopted the following technical scheme that.
A kind of galvanizing by dipping kalzium metal coating, the composition containing following percentage composition：Aluminium 4%-6.5%, calcium 0.1-0.8%,
Surplus is zinc and inevitable impurity；The impurity includes lead, cadmium, tin, antimony etc., total amount≤0.05%.
Preferably, above-mentioned galvanizing by dipping kalzium metal coating contains the composition of following percentage composition：Aluminium 4.5%-6%, calcium
0.3-0.5%, surplus is zinc and inevitable impurity.
The aluminium, calcium are added with zinc-aluminium intermediate alloy and aluminium-calcium intermediate alloy mode.
Above-mentioned galvanizing by dipping kalzium metal coating is prepared using following methods：Heating Zn, zinc-aluminium intermediate alloy to completely melt
Change, add aluminium-calcium intermediate alloy and be heated to being completely melt.
The hot dip coating method of above-mentioned galvanizing by dipping kalzium metal coating, comprises the following steps：The melting of alloy layer；Steel
The pretreatment of material matrix；Hot-dip；The temperature of the hot-dip is 430 DEG C -450 DEG C；Time is 10s-3min.
The method of smelting of the zinc-aluminium calcium alloy, comprises the following steps：Load weighted zinc, zinc-aluminium intermediate alloy are added
In smelting furnace, 500 DEG C are warming up to, addition aluminium-calcium intermediate alloy after being completely melt is waited, is warming up to 620 DEG C, waits and is dropped after being completely melt
Low temperature is to 430 DEG C -450 DEG C of hot-dip temperature.
The pretreatment, use following steps for：In 15wt% Na (OH)2Alkali cleaning oil removing in solution → clear water rinses →
Acid pickling and rust removing → clear water flushing → fluxing agent helps plating → drying in 10wt% hydrochloric acid.
In above-mentioned pretreatment, alkali cleaning temperature is 70-90 DEG C, time 3-5min；The pickling time is 3-5min；Help plating temperature
Spend for 70-90 DEG C, time 30s；Drying temperature is 100-120 DEG C, and the time is 2-3min.
A kind of fluxing agent of galvanizing by dipping kalzium metal coating, including following component：500g/L ZnCl2, 90g/L
SnCl2, 10g/L CeCl3, 7.5mL/L dodecyl sodium sulfates.
Near conventional hot dip temperature, solubility of the Ca in Zn or Al is not high, and solubility is with cooling procedure
And reduce, the sample after plating has fine intermetallic compounds precipitation in cooling procedure, forms crystallization nucleus, makes plating layer crystal
Grain refinement, improves corrosion resisting property.In addition, Ca and Mg have similar chemical property, adding in Zn-Al alloy can play similar
Effect, can adjust microcell acid-base property in Korrosionsmedium, improve corrosion resistance of the coating in containing Cl-environment.But Mg is added
When in zn-al alloy coating metal, the manufacturability of batch hot-dip is set to be deteriorated, coating is coarse, and is also easy to produce plating leakage, not yet can be into
Work(is applied to batch hot-dip.And without this harmful effect when adding Ca.With rare-earth phase ratio, rich contents of the Ca in the earth's crust, valency
Lattice are cheap, and Zn-Al-Ca alloys have than Zn-Al-RE（Galfan）More preferable corrosion resisting property.
The present invention has following advantageous benefits：The present invention galvanizing by dipping kalzium metal coating it is cheap, can batch heat
Immersion plating, hot plating technology are simple, good corrosion resistance, better than Zn-5%Al-RE；In terms of steel anti-corrosion, especially in heavy corrosion area
There is broad prospect of application.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the galvanizing by dipping kalzium metal coating of embodiment 1；
Fig. 2 is Fig. 1 partial enlargement photo；
Fig. 3 is bent for the Tafel polarization of the galvanizing by dipping kalzium metal coating, the hot dip galvanizing -5%Al-RE of comparative example 1 of embodiment 1
Line.
Embodiment
With reference to embodiment, the present invention will be further described with accompanying drawing, but the present invention is not limited by following embodiments
System.
Using Q345 steel as matrix material in all embodiments and comparative example, using machine cuts method be processed into 50mm ×
50mm × 3mm sheet specimens.
The galvanizing by dipping kalzium metal coating of embodiment 1
Weigh 500g ZnCl2, 90g SnCl2, 10g CeCl3It is dissolved in deionized water, adds 7.5mL dodecyl sodium sulfates,
Plus deionized water is to 1L, it is well mixed, is configured to fluxing agent.
Hot-dip is carried out in accordance with the following methods：
（1）Zinc-aluminium calcium alloy melting：Weigh pure Zn, 92g Zn-25%Al alloys of 878g to add in smelting furnace crucible, be warming up to 500
DEG C, wait completion to add 30g Al-10%Ca alloys after melting, then it is warming up to 620 DEG C, wait and stirred after being completely melt, reduction temperature is extremely
450 DEG C, that is, obtain 1kg Zn-5%Al-0.3%Ca alloys；
（2）The pretreatment of material matrix：In 15wt% Na (OH)2In solution 70 DEG C of alkali cleaning 5min oil removings → clear water rinse →
Pickling 5min derusting → clear water flushing → 70 DEG C of fluxing agent helps plating 30s → 120 DEG C to dry 3min in 10wt% hydrochloric acid；
（3）Hot-dip：By above-mentioned pretreated material matrix immersion Zn-5%Al-0.3%Ca aluminium alloys, 450 DEG C of hot-dips
30s.Sample is vertically proposed from molten alloy.Immersion and propose sample when, should push aside molten alloy surface oxide and
Scum silica frost.
With hang air cooling after sample proposition, hot-dip material S1 is obtained, its overlay coating stereoscan photograph is as schemed
1st, shown in Fig. 2：Surface topography be full eutectic structure, due to grain growth position to difference, some rich aluminium mutually be in sheet, some
Short cylinder is presented, rich aluminium phase mutually has phenomenon nested against one another with zinc-rich, corrosion product can be made to adhere better to coating surface, carried
The corrosion resistance of high coating.
Hot dip galvanizing -5%Al-0.1%RE the alloy layers of comparative example 1（Galfan）
（1）Melting Zn-5%Al-RE alloys.Weigh pure Zn, 164g Zn-25%Al alloys of 826g to add in smelting furnace, be warming up to
500 DEG C, wait completion to add 10g Al-10%RE alloys after melting, then be warming up to 620 DEG C, wait and stirred after being completely melt, reduction temperature
Degree obtains 1kg Zn-5%Al-0.1%RE alloys to 450 DEG C；
（2）The pretreatment of material matrix：In 15wt% Na (OH)2In solution 70 DEG C of alkali cleaning 5min oil removings → clear water rinse →
Pickling 5min derusting → clear water flushing → 70 DEG C of fluxing agent helps plating 30s → 120 DEG C to dry 3min in 10wt% hydrochloric acid；
（3）Hot-dip：By above-mentioned pretreated material matrix immersion Zn-5%Al-0.1%RE aluminium alloys, 450 DEG C of hot-dips
30s.Sample is vertically proposed from molten alloy.Immersion and propose sample when, should push aside molten alloy surface oxide and
Scum silica frost.
With hang air cooling after sample proposition, hot-dip material C 1 is obtained.
The electro-chemical test of the galvanizing by dipping kalzium metal coating material of embodiment 2
S1 and C1 corrosion potential and corrosion current is determined using Tafel extra curvatures pushing manipulation.
Tafel polarization test (using electrochemical workstation Parstat 2273) is carried out in 3.5%NaCl solution, is used
Three-electrode system：Working electrode（Sample）, reference electrode（Saturated calomel electrode）And auxiliary electrode（Platinized platinum）, each sample exists
Start test after immersion 30min, scanning range is relative to OCP -250mV ~ 250mV, sweep speed 0.5mV/s.
Fig. 3 is the S1 coating produced using or immersion herein（Zn-5%Al-0.3%Ca）With C1 coating（Zn-5%
Al-0.1%RE）Tafel polarization curves, be fitted by data, the corrosion potential of C1 coating is -1.06V, and corrosion current is 5.3
×10-5A/cm2, the corrosion potential of S1 coating is -1.07V, and corrosion current is 2.6 × 10-5A/cm2.The corrosion potential base of the two
This is consistent, but the corrosion current of Zn-5%Al-Ca coating is substantially reduced, thus with more preferable corrosion resistance.
The galvanizing by dipping kalzium metal coating of embodiment 3
Using the fluxing agent in embodiment 1, hot-dip is carried out in accordance with the following methods：
（1）Zinc-aluminium calcium alloy melting：Weigh pure Zn, 56g Zn-25%Al alloys of 904g to add in smelting furnace crucible, be warming up to 500
DEG C, wait completion to add 40g Al-10%Ca alloys after melting, then it is warming up to 620 DEG C, wait and stirred after being completely melt, reduction temperature is extremely
450 DEG C, that is, obtain 1kg Zn-5%Al-0.4%Ca alloys；
（2）The pretreatment of material matrix：In 15wt% Na (OH)2In solution 80 DEG C of alkali cleaning 4min oil removings → clear water rinse →
Pickling 4min derusting → clear water flushing → 80 DEG C of fluxing agent helps plating 30s → 100 DEG C to dry 3min in 10wt% hydrochloric acid；
（3）Hot-dip：By above-mentioned pretreated material matrix immersion Zn-5%Al-0.4%Ca aluminium alloys, 440 DEG C of hot-dips
50s.Sample is vertically proposed from molten alloy.Immersion and propose sample when, should push aside molten alloy surface oxide and
Scum silica frost.
With hang air cooling after sample proposition, hot-dip material S2 is obtained.
The galvanizing by dipping kalzium metal coating of embodiment 4
Using the fluxing agent in embodiment 1, hot-dip is carried out in accordance with the following methods：
（1）Zinc-aluminium calcium alloy melting：Weigh pure Zn, 20g Zn-25%Al alloys of 930g to add in smelting furnace crucible, be warming up to 500
DEG C, wait completion to add 50g Al-10%Ca alloys after melting, then it is warming up to 620 DEG C, wait and stirred after being completely melt, reduction temperature is extremely
450 DEG C, that is, obtain 1kg Zn-6%Al-0.5%Ca alloys；
（2）The pretreatment of material matrix：In 15wt% Na (OH)2In solution 90 DEG C of alkali cleaning 3min oil removings → clear water rinse →
Pickling 3min derusting → clear water flushing → 90 DEG C of fluxing agent helps plating 30s → 110 DEG C to dry 2min in 10wt% hydrochloric acid；
（3）Hot-dip：By above-mentioned pretreated material matrix immersion Zn-5%Al-0.5%Ca aluminium alloys, 430 DEG C of hot-dips
40s.Sample is vertically proposed from molten alloy.Immersion and propose sample when, should push aside molten alloy surface oxide and
Scum silica frost.
With hang air cooling after sample proposition, hot-dip material S3 is obtained.
Claims (9)
1. a kind of galvanizing by dipping kalzium metal coating, it is characterised in that the composition containing following percentage composition：Aluminium 4%-6.5%, calcium
0.1-0.8%, surplus is zinc and inevitable impurity.
2. galvanizing by dipping kalzium metal coating according to claim 1, it is characterised in that containing following percentage composition into
Point：Aluminium 4.5%-6%, calcium 0.3-0.5%, surplus are zinc and inevitable impurity.
3. according to any described galvanizing by dipping kalzium metal coating of claim 1 or 2, it is characterised in that the aluminium, calcium with
Zinc-aluminium intermediate alloy and aluminium-calcium intermediate alloy mode are added.
4. according to any described galvanizing by dipping kalzium metal coating of claim 1 or 2, it is characterised in that use following methods
Prepare：Heating Zn, zinc-aluminium intermediate alloy add aluminium-calcium intermediate alloy and are heated to being completely melt to produce to being completely melt.
5. a kind of hot dip coating method of the galvanizing by dipping kalzium metal coating as described in claim 1 or 2 is any, including following step
Suddenly：The melting of alloy layer, the pretreatment of ferrous materials matrix, hot-dip, it is characterised in that the temperature of the hot-dip is
430℃-450℃；Time is 10s-3min.
6. hot dip coating method according to claim 5, it is characterised in that the method for smelting of the zinc-aluminium calcium alloy, including
Following steps：Load weighted zinc, zinc-aluminium intermediate alloy are added in smelting furnace, 500 DEG C are warming up to, waits completion to be added after melting
Aluminium-calcium intermediate alloy, is warming up to 620 DEG C, and waiting reduces temperature to 430 DEG C -450 DEG C of hot-dip temperature after being completely melt.
7. hot dip coating method according to claim 5, it is characterised in that the pretreatment, use following steps for：
15wt% Na (OH)2Alkali cleaning oil removing in solution → clear water rinses → and acid pickling and rust removing → clear water is rinsed → is helped in 10wt% hydrochloric acid
Plating agent helps plating → drying.
8. hot dip coating method according to claim 7, it is characterised in that alkali cleaning temperature is 70-90 DEG C, time 3-5min；
The pickling time is 3-5min；It is 70-90 DEG C, time 30s to help plating temperature；Drying temperature is 100-120 DEG C, and the time is 2-
3min。
9. a kind of fluxing agent of galvanizing by dipping kalzium metal coating as claimed in claim 1, it is characterised in that including below into
Point：500g/L ZnCl2, 90g/L SnCl2, 10g/L CeCl3, 7.5mL/L dodecyl sodium sulfates.
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| CN201710541261.8A CN107177809A (en) | 2017-07-05 | 2017-07-05 | A kind of galvanizing by dipping kalzium metal coating and its hot dip coating method |
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| CN201710541261.8A CN107177809A (en) | 2017-07-05 | 2017-07-05 | A kind of galvanizing by dipping kalzium metal coating and its hot dip coating method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110592513A (en) * | 2019-09-30 | 2019-12-20 | 国网山东省电力公司临沂供电公司 | Hot-dip galvanizing aluminum-calcium alloy coating and hot-dip galvanizing method thereof |
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|---|---|---|---|---|
| JPH04288924A (en) * | 1991-03-16 | 1992-10-14 | Hitachi Cable Ltd | Steel wire coated with corrosion-resistant zinc alloy |
| CN101981219A (en) * | 2008-05-14 | 2011-02-23 | 安赛乐米塔尔研究与发展有限责任公司 | Method for producing a coated metal strip having an improved appearance |
| CN102703846A (en) * | 2012-06-12 | 2012-10-03 | 常州大学 | Hot dip coating Zn-Al-Zr alloy coating and hot dip coating method of hot dip coating Zn-Al-Zr alloy coating |
| CN103031505A (en) * | 2012-12-07 | 2013-04-10 | 山东电力集团公司电力科学研究院 | Plating aid of hot-dip galvanized aluminum magnesium alloy coating |
| CN104178719A (en) * | 2014-09-02 | 2014-12-03 | 国家电网公司 | Method for carrying out hot-dipping on aluminum-zinc alloy on steel surface |
-
2017
- 2017-07-05 CN CN201710541261.8A patent/CN107177809A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04288924A (en) * | 1991-03-16 | 1992-10-14 | Hitachi Cable Ltd | Steel wire coated with corrosion-resistant zinc alloy |
| CN101981219A (en) * | 2008-05-14 | 2011-02-23 | 安赛乐米塔尔研究与发展有限责任公司 | Method for producing a coated metal strip having an improved appearance |
| CN102703846A (en) * | 2012-06-12 | 2012-10-03 | 常州大学 | Hot dip coating Zn-Al-Zr alloy coating and hot dip coating method of hot dip coating Zn-Al-Zr alloy coating |
| CN103031505A (en) * | 2012-12-07 | 2013-04-10 | 山东电力集团公司电力科学研究院 | Plating aid of hot-dip galvanized aluminum magnesium alloy coating |
| CN104178719A (en) * | 2014-09-02 | 2014-12-03 | 国家电网公司 | Method for carrying out hot-dipping on aluminum-zinc alloy on steel surface |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110592513A (en) * | 2019-09-30 | 2019-12-20 | 国网山东省电力公司临沂供电公司 | Hot-dip galvanizing aluminum-calcium alloy coating and hot-dip galvanizing method thereof |
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Application publication date: 20170919 |