CN101619474B - Manufacturing method of zinc-nickel double-layer electroplating steel plate - Google Patents
Manufacturing method of zinc-nickel double-layer electroplating steel plate Download PDFInfo
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- CN101619474B CN101619474B CN2009100632585A CN200910063258A CN101619474B CN 101619474 B CN101619474 B CN 101619474B CN 2009100632585 A CN2009100632585 A CN 2009100632585A CN 200910063258 A CN200910063258 A CN 200910063258A CN 101619474 B CN101619474 B CN 101619474B
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Abstract
The invention discloses a manufacturing method of a zinc-nickel double-layer electroplating steel plate, which comprises the following steps: derusting a cold rolled steel plate or descaling a hot rolled steel plate, and cleaning the steel plate with water; activating the cleaned steel plate with diluted acid; electronickelling the activated steel plate, wherein a nickelling solution comprises the components of 240-280g/L of nickel sulfate, 40-65g/L of nickel chloride, 25-45g/L of boric acid and 1-3 g/L of acetic acid, and the pH value is controlled to be 4-4.5; annealing the steel plate by using hydrogen gas or nitrogen gas as a protective gas at the temperature of 550-650 DEG C, and forming a ferronickel alloy layer on the surface of the steel plate; then, electrogalvanizing the surface of the ferronickel alloy layer, wherein a galvanizing solution comprises the components of 250-300g/L of zinc sulfate, 1-2g/L of aluminum sulfate, 240-260g/L of sodium sulfate, 20-25g/L of boric acid and 2-3g/L of glucose, and the pH value is controlled to be 4.5-5.5; and washing the galvanized steel plate with water to acquire a finished product. Tests indicate that the corrosion resisting property of the acquired steel plate can be greatly improved, and a bonding force problem of a plating layer and a basal body is also solved.
Description
Technical field
The invention belongs to the electroplating technology field, be specifically related to a kind of manufacture method of zinc-nickel double-layer electroplating steel plate.
Background technology
To automobile, household electrical appliances steel plate,, adopt pot galvanize, electro-galvanizing at present both at home and abroad mostly in order to improve its corrosion resisting property.But pot galvanize existing problems: the one, coating uniformity is difficult to control, and coating is generally thicker, and resource consumption is more, and resource is caused waste; The 2nd, the bonding force of coating and matrix is relatively poor, adds and causes man-hour coating to come off sometimes carrying out deep-draw etc.Though electro-galvanizing has solved the homogeneity and the bonding force problem of coating, solidity to corrosion still is relatively poor.
Before the present invention, there have been some to improve the electroplated zinc nickel alloy process patent or the document of electroplating steel plate performance, patent DOUBLE LAYER ALLOYELECTROPLATED STEEL SHEET.JapanNo.JP4066693 as Japan, 1992-03-03 provides the first layer for containing Co 5～20%, weight is the Ni-Co alloy layer of 0.05～1.0g/m2, the second layer is for containing Ni 8～16%, has the Zn-Ni double-layer electroplating steel plate of corrosion resistance and surface luster preferably, but the electroplating steel plate of this invention only lays particular emphasis on the solidity to corrosion that improves coating, compare with galvanized pure zinc coating, the also corresponding raising of the hardness of its coating, thereby the bonding force of coating and matrix descends, and adds and might cause the coating local shedding man-hour carrying out deep-draw.The name of Sifang Surface Tech Co., Ltd., Nanjing is called " a kind of processing method of carrying out double zinc electroplating in the rolled steel plate continuous flow procedure ", the patent of invention that application number is 200610098271, the applying date is on December 8th, 2006 disclose method be rolled steel plate through pre-treatments such as oil removing, rust cleaning, activation after, at first entering the alkaline zinc plating groove electroplates, and then enter the acid zinc plating groove and electroplate, promptly on the alkaline zinc plating layer, deposit one deck acid zinc plating layer again, thereby reach a kind of double-deck zinc coating.The coating of its product and zinc-base harden and close close and firm, mainly solve the bonding force problem of coating and matrix or coating and top coat.
But the product of these methods can only lay particular emphasis on the problem in a certain respect in the bonding force problem of the solidity to corrosion that solves coating or coating and matrix or top coat, all can't not only improve the solidity to corrosion of coating but also can solve coating and the problem of the bonding force of matrix and top coat simultaneously.
Summary of the invention
Purpose of the present invention is exactly the manufacture method that a kind of zinc-nickel double-layer electroplating steel plate will be provided, utilize the electroplating steel plate of this method preparation not only to have good corrosion resisting property, and have good bonding force between coating and matrix and the top coat, have good pressworkability simultaneously.
For achieving the above object, manufacture method of the present invention comprises the steps:
1) cold-rolled steel sheet is carried out processing of rust removing or hot-rolled steel sheet is carried out de-scaling handle, wash;
2) steel plate after will cleaning activates with diluted acid;
3) steel plate after the activation is carried out electronickelling, the consisting of of the nickel plating aqueous solution: single nickel salt 240～280g/L, nickelous chloride 40～65g/L, boric acid 25～45g/L, acetic acid 1～3g/L, the pH value is controlled at 4～4.5;
4) then under 550～650 temperature, make protection gas with hydrogen or nitrogen steel plate is carried out anneal, form the Rhometal layer at surface of steel plate;
5) zinc-plated in the surface electrical of Rhometal layer again, the consisting of of the zinc-plated aqueous solution: zinc sulfate 250～300g/L, Tai-Ace S 150 1～2g/L, sodium sulfate 240～260g/L, boric acid 20～25g/L, glucose 2～3g/L, the pH value is controlled at 4.5～5.5;
6) steel plate after zinc-plated is washed, got product.
As improvement of the present invention, annealing time is controlled to be 0.3～3 hour in the described step 4).
As a further improvement on the present invention, in the described step 3) during electronickelling electroplating temperature be controlled to be 45～50 ℃, cathode current density is controlled to be: 2～5A/dm
2In the described step 5) during electro-galvanizing electroplating temperature be room temperature, cathode current density is controlled to be 0.8～3A/dm
2
Preferred plan of the present invention is that the electronickelling amount is controlled to be 0.4～2.5g/m in the described step 3)
2The electro-galvanizing amount is controlled to be 5～30g/m in the described step 5)
2
Manufacture method of the present invention is to plate one deck nickel earlier on the surface of steel plate, again the steel plate that is coated with nickel is heat-treated, form one deck layer of iron-nickel alloy at surface of steel plate, electro-galvanizing on layer of iron-nickel alloy then, the corrosion resisting property of steel plate was greatly enhanced, had solved the bonding force problem of coating and matrix again.The solidity to corrosion of this zinc-nickel double-layer electroplating steel plate is 4～6 times of identical thickness of coating electrogalvanizing steel plate, its solidity to corrosion is suitable with the zn-ni alloy deposits of identical thickness of coating, and the bonding force of its coating and matrix is good, thereby deep drawability can be better than the zn-ni alloy deposits steel plate.The zinc-nickel double-layer electroplating steel plate of the inventive method manufacturing need be specially adapted to automobile and household electrical appliances panel by electroplating the steel sheet that improve its corrosion resisting property applicable to auto sheet, tame electroplax and other.
Embodiment
Below in conjunction with several preferred embodiments preparation method of the present invention further is described in detail:
Embodiment 1
Sample adopts common cold-rolled steel sheet, is of a size of 200 * 200 * 0.5mm, and preparation process is as follows:
1) cold-rolled steel sheet carries out processing of rust removing, washes;
2) with the steel plate weight percent be the activation of 10% dilute hydrochloric acid again;
3) steel plate after will activating is sent into plating tank and is carried out electronickelling, the consisting of of this nickel plating aqueous solution: single nickel salt: 250g/L, and nickelous chloride: 45g/L, boric acid: 35g/L, acetic acid: 2g/L, pH4～4.5, temperature is controlled to be 45 ℃, and cathode current density is 2A/dm
2, the nickel plating amount is controlled to be: 0.4g/m
2
4) under 550 ℃ of temperature, anneal then, add nitrogen during annealing in the stove and make protection gas, to prevent the steel plate oxidation; Annealing time 0.3 hour is so that form layer of iron-nickel alloy at surface of steel plate.
5) zinc-plated in the surface electrical of layer of iron-nickel alloy again, the consisting of of the zinc-plated aqueous solution: zinc sulfate: 250g/L, Tai-Ace S 150: 1g/L, sodium sulfate: 250g/L, boric acid: 20g/L, glucose 2g/L, pH4.5, temperature is controlled to be room temperature, and cathode current density is 0.8A/dm
2, zinc-plated amount is controlled to be: 5g/m
2
6) after being washed, the steel plate after zinc-plated gets product.
Embodiment 2
Sample adopts common hot-rolled steel sheet, is of a size of 200 * 200 * 1.8mm, and preparation process is as follows:
1) hot-rolled steel sheet is carried out de-scaling and handle, wash;
2) with the steel plate weight percent be the activation of 10% dilute hydrochloric acid again;
3) steel plate after will activating is sent into plating tank and is carried out electronickelling, the consisting of of this nickel plating aqueous solution: single nickel salt: 240g/L, and nickelous chloride: 65g/L, boric acid: 25g/L, acetic acid: 1g/L, pH4～4.5, temperature is controlled to be 50 ℃, and cathode current density is 5A/dm
2, the nickel plating amount is controlled to be: 1.8g/m
2
4) then, under 650 ℃ of temperature, anneal, add hydrogen during annealing in the stove and go bail for and protect gas, to prevent the steel plate oxidation; Annealing time 1 hour is so that form layer of iron-nickel alloy at surface of steel plate.
5) zinc-plated in the surface electrical of layer of iron-nickel alloy again, the consisting of of this zinc-plated aqueous solution: zinc sulfate: 260g/L, Tai-Ace S 150: 1.5g/L, sodium sulfate: 260g/L, boric acid: 25g/L, glucose 2.5g/L, pH5, temperature is controlled to be room temperature, and cathode current density is 2A/dm
2, zinc-plated amount is controlled to be: 10g/m
2
6) after being washed, the steel plate after zinc-plated gets product.
Embodiment 3
Sample adopts common cold-rolled steel sheet, is of a size of 200 * 200 * 1.2mm, and preparation process is as follows:
1) cold-rolled steel sheet carries out processing of rust removing, washes;
2) with the steel plate weight percent be the activation of 20% dilute sulphuric acid again;
3) steel plate after will activating enters plating tank and carries out electronickelling, the consisting of of this nickel plating aqueous solution: single nickel salt: 280g/L, and nickelous chloride: 40g/L, boric acid: 40g/L, acetic acid: 3g/L, pH4.5, temperature is controlled to be 45 ℃, and cathode current density is 3A/dm
2, the nickel plating amount is controlled to be: 1.2g/m
2
4) then, under 600 ℃ of temperature, anneal, add hydrogen during annealing in the stove and go bail for and protect gas, to prevent the steel plate oxidation; Annealing time 2 hours is so that form layer of iron-nickel alloy at surface of steel plate.
5) zinc-plated in the surface electrical of layer of iron-nickel alloy again, the consisting of of this zinc-plated aqueous solution: zinc sulfate: 300g/L, Tai-Ace S 150: 2g/L, sodium sulfate: 240g/L, boric acid: 22g/L, glucose 3g/L, pH5.5, temperature is controlled to be room temperature, and cathode current density is 3A/dm
2, zinc-plated amount is controlled to be: 16g/m
2
6) after being washed, the steel plate after zinc-plated gets product.
Embodiment 4
Sample adopts common cold-rolled steel sheet, is of a size of 200 * 200 * 1.2mm, and preparation process is as follows:
1) cold-rolled steel sheet carries out processing of rust removing, washes;
2) with the steel plate weight percent be the activation of 10% dilute hydrochloric acid again;
3) steel plate after will activating enters plating tank and carries out electronickelling, the consisting of of this nickel plating aqueous solution: single nickel salt: 250g/L, and nickelous chloride: 55g/L, boric acid: 36g/L, acetic acid: 2.6g/L, pH4.5, temperature is controlled to be 45 ℃, and cathode current density is 4A/dm
2, the nickel plating amount is controlled to be: 2.5g/m
2
4) then, under 620 ℃ of temperature, anneal, add nitrogen during annealing in the stove and make protection gas, to prevent the steel plate oxidation; Annealing time 3 hours is so that form layer of iron-nickel alloy at surface of steel plate.
5) zinc-plated in the surface electrical of layer of iron-nickel alloy again, the consisting of of this zinc-plated aqueous solution: zinc sulfate: 280g/L, Tai-Ace S 150: 1.8g/L, sodium sulfate: 250g/L, boric acid: 21g/L, glucose 3g/L, pH5.5, temperature is controlled to be room temperature, and cathode current density is 3A/dm
2, zinc-plated amount is controlled to be: 30g/m
2
6) after being washed, the steel plate after zinc-plated gets product.
Embodiment 5
Sample adopts common cold-rolled steel sheet, is of a size of 200 * 200 * 1.5mm, and preparation process is as follows:
1) cold-rolled steel sheet carries out processing of rust removing, washes;
2) with the steel plate weight percent be the activation of 20% dilute sulphuric acid again;
3) steel plate after will activating enters plating tank and carries out electronickelling, the consisting of of this nickel plating aqueous solution: single nickel salt: 265g/L, and nickelous chloride: 50g/L, boric acid: 45g/L, acetic acid: 2.5g/L, pH4～4.5, temperature is controlled to be 45 ℃, and cathode current density is 3.5A/dm
2, the nickel plating amount is controlled to be: 2.0g/m
2
4) then, under 650 ℃ of temperature, anneal, add nitrogen during annealing in the stove and make protection gas, to prevent the steel plate oxidation; Annealing time 2.5 hours is so that form layer of iron-nickel alloy at surface of steel plate.
5) zinc-plated in the surface electrical of layer of iron-nickel alloy again, the consisting of of this zinc-plated aqueous solution: zinc sulfate: 280g/L, Tai-Ace S 150: 1.5g/L, sodium sulfate: 250g/L, boric acid: 23g/L, glucose 3g/L, pH5.5, temperature is controlled to be room temperature, and cathode current density is 2.5A/dm
2, zinc-plated amount is controlled to be: 25g/m
2
6) after being washed, the steel plate after zinc-plated gets product.
Zinc-nickel double-layer electroplating steel plate with above-mentioned five embodiment carries out salt fog accelerated corrosion test, folding test and ball indentation test with the electrolytic galvanized sheet and the electroplated zinc nickel alloy Coated Steel of identical thickness of coating respectively.Experimental result is that the salt spray corrosion resistance of the zinc-nickel double-layer electroplating steel plate of embodiment 1,2,3,4,5 is respectively 4.5 times, 5.5 times, 6 times, 5.5 times, 5 times of steel plate galvanized; The salt spray corrosion resistance of five embodiment products is suitable with the electroplated zinc nickel alloy Coated Steel; And the binding force of cladding material of measuring by folding test and ball indentation test, five embodiment products are better than the zn-ni alloy deposits steel plate and identical with electrogalvanizing steel plate.
Claims (5)
1. the manufacture method of a zinc-nickel double-layer electroplating steel plate, it is characterized in that: it may further comprise the steps:
1) cold-rolled steel sheet is carried out processing of rust removing or hot-rolled steel sheet is carried out de-scaling handle, wash;
2) steel plate after will cleaning activates with diluted acid;
3) steel plate after the activation is carried out electronickelling, the consisting of of the nickel plating aqueous solution: single nickel salt 240～280g/L, nickelous chloride 40～65g/L, boric acid 25～45g/L, acetic acid 1～3g/L, the pH value is controlled at 4～4.5;
4) then under 550～650 ℃ of temperature, make protection gas with hydrogen or nitrogen steel plate is carried out anneal, form the Rhometal layer at surface of steel plate;
5) zinc-plated in the surface electrical of Rhometal layer again, the consisting of of the zinc-plated aqueous solution: zinc sulfate 250～300g/L, Tai-Ace S 150 1～2g/L, sodium sulfate 240～260g/L, boric acid 20～25g/L, glucose 2～3g/L, the pH value is controlled at 4.5～5.5;
6) steel plate after zinc-plated is washed, got product.
2. the manufacture method of zinc-nickel double-layer electroplating steel plate according to claim 1, it is characterized in that: in the described step 3), the temperature of electronickelling is controlled at 45～50 ℃, and cathode current density is controlled at: 2～5A/dm
2In the described step 5), the temperature of electro-galvanizing is controlled at room temperature, and cathode current density is controlled at 0.8～3A/dm
2
3. the manufacture method of zinc-nickel double-layer electroplating steel plate according to claim 1 and 2, it is characterized in that: in the described step 3), the electronickelling amount is controlled at 0.4～2.5g/m
2, in the described step 5), the electro-galvanizing amount is controlled at 5～30g/m
2
4. the manufacture method of zinc-nickel double-layer electroplating steel plate according to claim 1 and 2, it is characterized in that: in the described step 4), annealing time is controlled at 0.3～3h.
5. the manufacture method of zinc-nickel double-layer electroplating steel plate according to claim 3, it is characterized in that: in the described step 4), annealing time is controlled at 0.3～3h.
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| JP4883240B1 (en) * | 2010-08-04 | 2012-02-22 | Ｊｆｅスチール株式会社 | Steel sheet for hot press and method for producing hot press member using the same |
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| WO2016125741A1 (en) | 2015-02-03 | 2016-08-11 | 新日鐵住金株式会社 | Steel plate for use in fuel tank |
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