CN102560307A - Production process of multiple aluminum zinc alloy hot-dipped on surface of carbon steel - Google Patents
Production process of multiple aluminum zinc alloy hot-dipped on surface of carbon steel Download PDFInfo
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Abstract
The invention relates to a production process of multiple aluminum zinc alloy hot-dipped on the surface of carbon steel, which comprises the following steps of: pickling, assisting in plating, drying, hot-dipping and passivating. Hot-dipping liquid comprises the following components in percentage by weight: 6-8 weight percent of aluminum, 1.2-2.5 weight percent of nickel, 0.5-1.2 weight percent of silicon, 0.5-1.5 weight percent of magnesium, 0.5-0.9 weight percent of manganese, 1.2-1.5 weight percent of titanium and the balance of zinc; and passivating liquid comprises the following components in percentage by weight: 0.3-0.5 weight percent of titanium nitrate, 1.2-2.0 weight percent of hydrogen peroxide, 0.3-0.6 weight percent of phosphoric acid and 0.8-1.2 weight percent of citric acid. With the adoption of the production process, a hot-dipping carbon steel material which is excellent in corrosion resistance and particularly is excellent in corrosion resistance under humid environment can be prepared, and a prepared passivating protective film is uniform, level and compact and can effectively prevent the isolation of corrosion environment from zinc coating and effectively restrain the corrosion.
Description
Technical field
The present invention relates to a kind of or immersion, specifically, the present invention relates to a kind of production technique at the steel surface hot dipped multi-element Al-Zn alloy.
Background technology
Existing hot-dip aluminizing-zinc/silicon alloy steel plate is widely used in China, though its over-all properties such as corrosion-resistant will improve nearly 5-6 doubly than pure galvanizing, for the more use under the severe environment in buried pipeline, ocean etc., its corrosion resistance nature still has much room for improvement.The hot dipped multi-element Al-Zn alloy that relates in the prior art mainly comprises aluminium, silicon, rare earth and surplus zinc composition, can also comprise that certain proportion of additive is elementary composition as adding zirconium, boron, titanium etc.Add the corrosion resistance nature that elements such as zirconium, boron, titanium can improve aluminium-zinc alloy.
In addition,, influence the outward appearance of product under wet environment, also can reduce the work-ing life of galvanized workpiece because hot galvanized layer is prone to corrode.Present most popular anti-corrosion method is the lower concentration chromating; The advantage of its passivation is: chromate passivation film has solidity to corrosion and smooth densification; With the firm binding force of matrix metal, in the corrosive environment, matrix metal played the effect of insulation blocking; And contain the solubility hexavalent chromium compound in the chromate passivation film, can play restraining effect to further corrosion, promptly usually said " self-healing ability " to the zinc passivation once more of naked leak.But sexavalent chrome toxicity is very big, serious harm HUMAN HEALTH and environment and used by strict restriction.The domestic and international non-chromium inactivating technique of reporting mainly contains molybdate and rare earth metal salt passivation, silicate passivation, vannadate passivation, titanium salt passivation, organism passivation and tungstate passivation etc. at present; But the corrosion resisting property of these Chrome-free conversion films is compared with chromate conversion coating and is also had a certain distance; Though the compound conversion film corrosion resisting property of part near or surpass chromate conversion coating; But the treatment process more complicated, cost is too high.
Summary of the invention
In order further to improve the corrosion resistance nature of pot galvanize carbon steel, the invention provides the production technique of superloy surface hot dipped multi-element Al-Zn alloy.
Technical problem to be solved by this invention is to realize through following technical scheme:
The production technique of superloy surface hot dipped multi-element Al-Zn alloy comprises acid pickling step, helps plating step, baking step, hot dip step and passivation, step, it is characterized in that the described auxiliary agent that helps the plating step to adopt is: the NH of 8-10wt%
4The ZnCl of Cl, 3-5wt%
2, 3-5wt% MnCl
2, the NaF of 2-3wt% and the water of surplus, helping the plating temperature is 63-68 ℃, helping the plating time is 70-120 second; Adopt hot-air seasoning in the described baking step, temperature is controlled at 95-105 ℃, and the time is 10-15 minute; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 6-8wt% aluminium, 1.2-2.5wt%, 0.5-1.2wt% silicon, 0.5-1.5wt% magnesium, 0.5-0.9wt%, the titanium of 1.2-1.5wt% and the zinc of surplus; The hot dip process liquid temp is 425-439 ℃, and the immersion plating time is 3.5-5min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.3-0.5wt%, the hydrogen peroxide of 1.2-2.0wt%, the phosphoric acid of 0.3-0.6wt%, the Hydrocerol A of 0.8-1.2wt%; The Passivation Treatment temperature is 20-25 ℃, and the Passivation Treatment time is 1.5-2.5min.
Preferably, in said production technique, the pickle solution that adopts in the described acid pickling step is the hydrogen fluoride of 0.3-0.5wt%, the hydrogenchloride of 1.5-2.0wt%, the nitric acid of 0.3-0.5wt%, the urotropine of 0.3-0.6wt% and the water of surplus; Pickling temperature is 15-25 ℃, and the pickling time is 18-25min.
Adopt technology of the present invention can prepare excellent corrosion resistance; Especially the hot dip process carbon steel material of corrosion resistance excellent in wet environment; And even, the smooth densification of prepared passivation protection film can effectively prevent to isolate corrosive environment and zinc coating, can effectively suppress corrosion.
Specific embodiment
In order further to understand the present invention, bright specifically below in conjunction with embodiment to the present invention's work, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Be example with Q235 steel and No. 45 steel commonly used in the present invention, detect corrosion resisting property through the carbon steel after the hot dip process processing.The present invention adopts the neutral salt spray corrosion test method to estimate the coating corrosion resistance nature, uses YWX/Q-150 type centrifugal sale mist testing chamber, according to GB6458-86 sample is carried out neutral salt spray test.Etchant solution is 5% (weight) NaCl aqueous solution, and the pH value is 6.5～7.0, and temperature is (35 ± 2) ℃ in the spray box, and sinkability is 2mL/ (80cm
2H), sample becomes 25～30 ° of placements with vertical direction; The edge of sample applies sealing to avoid side effect with organic gel; Sample every day continuously spray 8h, to stop 16h be one-period; The used time of 5% white rust occurs with coating surface and estimate the solidity to corrosion of coating.
Embodiment 1
Production technique at No. 45 steel surface hot dipped multi-element Al-Zn alloys; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.3wt%, the hydrogenchloride of 1.5wt%, the nitric acid of 0.3wt%, the urotropine of 0.5wt% and the water of surplus; Pickling temperature is 25 ℃, and the pickling time is 18min; The described auxiliary agent that helps the plating step to adopt is: the NH of 8wt%
4The ZnCl of Cl, 3wt%
2, 3wt% MnCl
2, the NaF of 3wt% and the water of surplus, helping the plating temperature is 68 ℃, helping the plating time is 100 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 100 ℃, and the time is 10 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 6wt% aluminium, 1.2wt%, 1.2wt% silicon, 0.5wt% magnesium, 0.9wt%, the titanium of 1.2wt% and the zinc of surplus; The hot dip process liquid temp is 435 ℃, and the immersion plating time is 5min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.3wt%, the hydrogen peroxide of 1.2wt%, the phosphoric acid of 0.5wt%, the Hydrocerol A of 0.8wt%, and the Passivation Treatment temperature is 25 ℃, and the Passivation Treatment time is 1.5min.
Embodiment 2
Production technique at Q235 steel surface hot dipped multi-element Al-Zn alloy; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.3wt%, the hydrogenchloride of 1.5wt%, the nitric acid of 0.3wt%, the urotropine of 0.5wt% and the water of surplus; Pickling temperature is 25 ℃, and the pickling time is 18min; The described auxiliary agent that helps the plating step to adopt is: the NH of 8wt%
4The ZnCl of Cl, 3wt%
2, 3wt% MnCl
2, the NaF of 3wt% and the water of surplus, helping the plating temperature is 68 ℃, helping the plating time is 100 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 100 ℃, and the time is 10 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 6wt% aluminium, 1.2wt%, 1.2wt% silicon, 0.5wt% magnesium, 0.9wt%, the titanium of 1.2wt% and the zinc of surplus; The hot dip process liquid temp is 435 ℃, and the immersion plating time is 5min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.3wt%, the hydrogen peroxide of 1.2wt%, the phosphoric acid of 0.5wt%, the Hydrocerol A of 0.8wt%, and the Passivation Treatment temperature is 25 ℃, and the Passivation Treatment time is 1.5min.
Embodiment 3
Production technique at No. 45 steel surface hot dipped multi-element Al-Zn alloys; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.5wt%, the hydrogenchloride of 2.0wt%, the nitric acid of 0.3wt%, the urotropine of 0.6wt% and the water of surplus; Pickling temperature is 15 ℃, and the pickling time is 25min; The described auxiliary agent that helps the plating step to adopt is: the NH of 10wt%
4The ZnCl of Cl, 5wt%
2, 5wt% MnCl
2, the NaF of 2wt% and the water of surplus, helping the plating temperature is 63 ℃, helping the plating time is 120 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 95 ℃, and the time is 15 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 8wt% aluminium, 2.5wt%, 0.5wt% silicon, 1.5wt% magnesium, 0.5wt%, the titanium of 1.5wt% and the zinc of surplus; The hot dip process liquid temp is 430 ℃, and the immersion plating time is 4min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.5wt%, the hydrogen peroxide of 2.0wt%, the phosphoric acid of 0.3wt%, the Hydrocerol A of 1.2wt%, and the Passivation Treatment temperature is 20 ℃, and the Passivation Treatment time is 2.5min.
Embodiment 4
Production technique at No. 45 steel surface hot dipped multi-element Al-Zn alloys; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.5wt%, the hydrogenchloride of 2.0wt%, the nitric acid of 0.3wt%, the urotropine of 0.6wt% and the water of surplus; Pickling temperature is 15 ℃, and the pickling time is 25min; The described auxiliary agent that helps the plating step to adopt is: the NH of 10wt%
4The ZnCl of Cl, 5wt%
2, 5wt% MnCl
2, the NaF of 2wt% and the water of surplus, helping the plating temperature is 63 ℃, helping the plating time is 120 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 95 ℃, and the time is 15 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 8wt% aluminium, 2.5wt%, 0.5wt% silicon, 1.5wt% magnesium, 0.5wt%, the titanium of 1.5wt% and the zinc of surplus; The hot dip process liquid temp is 430 ℃, and the immersion plating time is 4min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.5wt%, the hydrogen peroxide of 2.0wt%, the phosphoric acid of 0.3wt%, the Hydrocerol A of 1.2wt%, and the Passivation Treatment temperature is 20 ℃, and the Passivation Treatment time is 2.5min.
Comparative example 1
Production technique at No. 45 steel surface hot dipped multi-element Al-Zn alloys; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.3wt%, the hydrogenchloride of 1.5wt%, the nitric acid of 0.3wt%, the urotropine of 0.5wt% and the water of surplus; Pickling temperature is 25 ℃, and the pickling time is 18min; The described auxiliary agent that helps the plating step to adopt is: the NH of 8wt%
4The ZnCl of Cl, 3wt%
2, 3wt% MnCl
2, the NaF of 3wt% and the water of surplus, helping the plating temperature is 68 ℃, helping the plating time is 100 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 100 ℃, and the time is 10 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 6wt% aluminium, 1.2wt%, 1.2wt% silicon, 0.5wt% magnesium, 0.9wt%, the titanium of 1.2wt% and the zinc of surplus; The hot dip process liquid temp is 435 ℃, and the immersion plating time is 5min.
Comparative example 2
Production technique at Q235 steel surface hot dipped multi-element Al-Zn alloy; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.3wt%, the hydrogenchloride of 1.5wt%, the nitric acid of 0.3wt%, the urotropine of 0.5wt% and the water of surplus; Pickling temperature is 25 ℃, and the pickling time is 18min; The described auxiliary agent that helps the plating step to adopt is: the NH of 8wt%
4The ZnCl of Cl, 3wt%
2, 3wt% MnCl
2, the NaF of 3wt% and the water of surplus, helping the plating temperature is 68 ℃, helping the plating time is 100 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 100 ℃, and the time is 10 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 6wt% aluminium, 1.2wt%, 1.2wt% silicon, 0.5wt% magnesium, 0.9wt%, the titanium of 1.2wt% and the zinc of surplus; The hot dip process liquid temp is 435 ℃, and the immersion plating time is 5min.
Comparative example 3
Production technique at No. 45 steel surface hot dipped multi-element Al-Zn alloys; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.5wt%, the hydrogenchloride of 2.0wt%, the nitric acid of 0.3wt%, the urotropine of 0.6wt% and the water of surplus; Pickling temperature is 15 ℃, and the pickling time is 25min; The described auxiliary agent that helps the plating step to adopt is: the NH of 10wt%
4The ZnCl of Cl, 5wt%
2, the NaF of 2wt% and the water of surplus, helping the plating temperature is 63 ℃, helping the plating time is 120 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 95 ℃, and the time is 15 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the zinc of 8wt% aluminium, 0.5wt% silicon and surplus; The hot dip process liquid temp is 430 ℃, and the immersion plating time is 4min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.5wt%, the hydrogen peroxide of 2.0wt%, the phosphoric acid of 0.3wt%, the Hydrocerol A of 1.2wt%, and the Passivation Treatment temperature is 20 ℃, and the Passivation Treatment time is 2.5min.
Comparative example 4
Production technique at No. 45 steel surface hot dipped multi-element Al-Zn alloys; Comprise acid pickling step, help plating step, baking step, hot dip step and passivation, step, the pickle solution that adopts in the wherein said acid pickling step is the hydrogen fluoride of 0.5wt%, the hydrogenchloride of 2.0wt%, the nitric acid of 0.3wt%, the urotropine of 0.6wt% and the water of surplus; Pickling temperature is 15 ℃, and the pickling time is 25min; The described auxiliary agent that helps the plating step to adopt is: the NH of 10wt%
4The ZnCl of Cl, 5wt%
2, the NaF of 2wt% and the water of surplus, helping the plating temperature is 63 ℃, helping the plating time is 120 seconds; Adopt hot-air seasoning in the described baking step, temperature is controlled at 95 ℃, and the time is 15 minutes; The hot dipping plating bath that adopts in the described hot dip step is: the zinc of 8wt% aluminium, 0.5wt% silicon and surplus; The hot dip process liquid temp is 430 ℃, and the immersion plating time is 4min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.5wt%, the hydrogen peroxide of 2.0wt%, the phosphoric acid of 0.3wt%, the Hydrocerol A of 1.2wt%, and the Passivation Treatment temperature is 20 ℃, and the Passivation Treatment time is 2.5min.
Embodiment 1-4 and the resulting hot dip process carbon steel of comparative example 1-4 are carried out above-mentioned neutral salt spray test, and the time that 5% white rust appears in coating surface was respectively 155 hours, 152 hours, 168 hours, 163 hours, 32 hours, 25 hours, 82 hours and 87 hours.Can prove that by above-mentioned experiment the carbon steel of handling through or immersion of the present invention has excellent corrosion resisting property, and through the scene on the spot simulation test show that also resulting hot dip process carbon steel has excellent corrosion resisting property and endurance quality under severe environment such as humidity.
The above; Be merely the preferred embodiments of the present invention; Can not be interpreted as with this and limit scope of the present invention, the embodiment of all distortion of in claims of the present invention require the scope of protection, being made that is equal to and change is all in the present invention's scope required for protection.
Claims (2)
1. the production technique of superloy surface hot dipped multi-element Al-Zn alloy comprises acid pickling step, helps plating step, baking step, hot dip step and passivation, step, it is characterized in that the described auxiliary agent that helps the plating step to adopt is: the NH of 8-10wt%
4The ZnCl of Cl, 3-5wt%
2, 3-5wt% MnCl
2, the NaF of 2-3wt% and the water of surplus, helping the plating temperature is 63-68 ℃, helping the plating time is 70-120 second; Adopt hot-air seasoning in the described baking step, temperature is controlled at 95-105 ℃, and the time is 10-15 minute; The hot dipping plating bath that adopts in the described hot dip step is: the manganese of the nickel of 6-8wt% aluminium, 1.2-2.5wt%, 0.5-1.2wt% silicon, 0.5-1.5wt% magnesium, 0.5-0.9wt%, the titanium of 1.2-1.5wt% and the zinc of surplus; The hot dip process liquid temp is 425-439 ℃, and the immersion plating time is 3.5-5min; The passivating solution that adopts in the described passivation, step is the Titanium Nitrate of 0.3-0.5wt%, the hydrogen peroxide of 1.2-2.0wt%, the phosphoric acid of 0.3-0.6wt%, the Hydrocerol A of 0.8-1.2wt%; The Passivation Treatment temperature is 20-25 ℃, and the Passivation Treatment time is 1.5-2.5min.
2. according to the production technique of the steel surface hot dipped multi-element Al-Zn alloy of claim 1, it is characterized in that the pickle solution that adopts in the described acid pickling step is the hydrogen fluoride of 0.3-0.5wt%, the hydrogenchloride of 1.5-2.0wt%, the nitric acid of 0.3-0.5wt%, the urotropine of 0.3-0.6wt% and the water of surplus; Pickling temperature is 15-25 ℃, and the pickling time is 18-25min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103981474A (en) * | 2014-05-13 | 2014-08-13 | 国家电网公司 | Highly anti-corrosion zinc-based alloy plating used for solvent method hot dipping of steel |
| CN105803373A (en) * | 2016-05-17 | 2016-07-27 | 赤峰广圆电力铁塔制造有限公司 | Cooling-passivating solution after hot-dip galvanizing, and hot-dip galvanizing and cooling-passivating process |
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| CN101045980A (en) * | 2007-04-23 | 2007-10-03 | 刘国林 | High aluminium zinc alloy hot dip coating process for iron steel product |
| CN101665895A (en) * | 2009-09-11 | 2010-03-10 | 广西大学 | Composite method of plating steel by hot dipping |
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| CN101045980A (en) * | 2007-04-23 | 2007-10-03 | 刘国林 | High aluminium zinc alloy hot dip coating process for iron steel product |
| CN101665895A (en) * | 2009-09-11 | 2010-03-10 | 广西大学 | Composite method of plating steel by hot dipping |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103981474A (en) * | 2014-05-13 | 2014-08-13 | 国家电网公司 | Highly anti-corrosion zinc-based alloy plating used for solvent method hot dipping of steel |
| CN103981474B (en) * | 2014-05-13 | 2017-07-21 | 国家电网公司 | A kind of high anticorrosive zinc base alloy layer for steel solvent method hot-dip |
| CN105803373A (en) * | 2016-05-17 | 2016-07-27 | 赤峰广圆电力铁塔制造有限公司 | Cooling-passivating solution after hot-dip galvanizing, and hot-dip galvanizing and cooling-passivating process |
| CN105803373B (en) * | 2016-05-17 | 2018-09-28 | 赤峰广圆电力铁塔制造有限公司 | Galvanizing postcooling passivating solution and galvanizing cool down passivation technology |
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