CN102206842B - Manufacturing method of zinc/tin double-layer electroplated steel plate - Google Patents
Manufacturing method of zinc/tin double-layer electroplated steel plate Download PDFInfo
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- CN102206842B CN102206842B CN2011101155449A CN201110115544A CN102206842B CN 102206842 B CN102206842 B CN 102206842B CN 2011101155449 A CN2011101155449 A CN 2011101155449A CN 201110115544 A CN201110115544 A CN 201110115544A CN 102206842 B CN102206842 B CN 102206842B
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Abstract
The invention discloses a manufacturing method of a zinc/tin double-layer electroplated steel plate, which comprises the following steps: carrying out acid washing on a low-carbon cold-rolled steel plate, removing rust, degreasing, cleaning, and activating with dilute acid; electrogalvanizing the activated steel plate; washing the surface of the electrogalvanized steel plate with water, and carrying out tin electroplating; cleaning the sample with water, carrying out soft heating on the tin-electroplated plate with a resistance soft-heating furnace, carrying out water quenching, cleaning with soda, and carrying out cathodic passivation with chromate; and washing the passivated zinc/tin double-layer electroplated steel plate with water, and carrying out blow-drying to obtain the finished product. The zinc/tin double-layer electroplated steel plate prepared by the method disclosed by the invention has the advantages of beautiful appearance, no toxicity, environmental protection and low cost; and the corrosion resistance of the zinc/tin double-layer electroplated steel plate is equivalent to that of a tin-electroplated steel plate.
Description
Technical field
The invention belongs to the electroplating technology field, be specifically related to a kind of method of manufacture of zinc-tin double-layer electroplating steel plate.
Background technology
Because tin is nontoxic, human body is safe from harm, so people make food cans and beverages can with tin plate.Tin plate the earliest is the method that adopts hot tinning, is about to tin and again tin is coated on surface of steel plate after with high temperature melting, and the tin plate of making in this way is because the tin layer is thicker, and homogeneity is relatively poor, so cost is very high.Along with progress of science and technology, people adopted electric plating method the tin layer to be deposited to the surface of steel plate through the method for galvanic deposit afterwards.The tin layer of electrolytic tinplate is even, and the thickness of tin is compared significantly attenuate with hot tinning, and cost significantly reduces.But because of the present still a kind of comparatively valuable metal of tin, along with the user requires increasingly highly to the control of cost, the use of further saving the tin amount becomes the primary means that reduce cost.
A kind of method of saving the tin amount is exactly directly to reduce the thickness of tin coating; The benefit of doing like this is that technology is not done change basically; And the product characteristics that can keep beautiful outward appearance of tin plate and asepsis environment-protecting, and relatively environmental protection of this technology itself, less to human body and environmental damage.But the corrosion resisting property of tin plate can descend behind the tin coating attenuate, excessively falls tin even can influence its normal use.In order both to save precious metal tin; Improve the steel plate corrosion resistance nature again; The permanent husband of the universe of Japan Japan steel plate has introduced the TFS steel plate in " plate for surface treatment plate for can " at 1988 " practice sufacing " on the first phase, this TFS steel plate is that electrolytic chromate is handled steel plate, also is tin free steel sheet; It is the chromate film of being made up of chromium metal and hydrated chromium oxide compound at surface of steel plate formation one deck through the method for galvanic deposit, and the thickness of chromate film is 100mg/m
2About.The TFS steel plate is applied to beverages can and various bottle cap at first, and people produced the pad pasting steel plate on the surface of TFS steel plate through the method for pad pasting again afterwards, and this pad pasting steel plate is widely used in beverages can and food cans in Japan at present.Though TFS steel plate and fine at the steel plate corrosion resistance nature of TFS surface of steel plate pad pasting, because therefore its still hexavalent chromate of using in carrying out filling a prescription when electrolytic chromate is handled can cause bigger infringement and environment is caused bigger pollution human body; The pad pasting steel plate also is unfavorable for welding processing in carrying out the Three piece Can system jar course of processing in addition.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of manufacture of zinc-tin double-layer electroplating steel plate, and the electroplating steel plate that this method is made is few with the tin amount, and cost is lower, and environmental protection is attractive in appearance, and corrosion resistance nature is better.
For solving the problems of the technologies described above, the method for manufacture that the present invention adopts comprises the steps:
1) the low-carbon cold rolling steel plate is carried out pickling, rust cleaning, degreasing, cleans and handle, and use the diluted acid activation;
2) steel plate after the activation is carried out electro-galvanizing, the consisting of of galvanizing solution: zinkosite is 475～495g/L, and Patent alum is 28～32g/L, and sodium sulfate is 48～52g/L, and alum is 45～50g/L, and the pH value is 3.8～4.3;
The surface of steel plate that 3) will plate behind the zinc washes, and carries out eleetrotinplate then, the consisting of of tin plating solution: stannous fluoboric acid is 190～210g/L, and free fluorine boric acid is 100～200g/L, and gelatin is 5～6g/L, and β-Nai Fen is 0.9～1.1g/L;
4) plated tin after water sample is cleaned up, with resistance soft heat stove tin plate is carried out then that soft heat, hardening, soda are cleaned, the passivation of chromic salt negative electrode, passivating solution consists of: sodium dichromate 99 is 20～25g/L, the pH value is 4～5;
5) the zinc-tin double-layer electroplating steel plate that passivation is finished is washed, is dried up, and gets product.
As to improvement of the present invention, said step 2) in, the temperature of electro-galvanizing is a room temperature, cathode current density is 1～3A/dm
2, in the said step 3), the temperature of eleetrotinplate is 25～35 ℃, cathode current density is 3～12A/dm
2
As to further improvement of the present invention, in the said step 4), passivation temperature is 60～65 ℃, and electrochemistry negative electrode passivation electric weight is not less than 2.5C/dm
2
Preferred plan of the present invention is said step 2) in, the electro-galvanizing amount is 1.0～6.0g/m
2, in the said step 3), the eleetrotinplate amount is 1.0～6.0g/m
2, in the said step 4), during the negative electrode passivation in the passive film chrome content be 5～8mg/m
2
Method of manufacture of the present invention is to plate one deck zinc earlier at the low-carbon cold rolling surface of steel plate, again the steel plate that is coated with zinc is carried out eleetrotinplate and handles, and forms the zinc-tin double-layer electroplating steel plate.Because the price of zinc is more much lower than the price of tin, and the resource of zinc is abundanter than tin, therefore, the zinc-tin double-layer electroplating steel plate of producing is like this compared with the pure tin coating steel plate of same thickness, and cost can significantly reduce; Because zinc is the same with tin to have excellent corrosion resisting performance, so the pure tin coating steel plate corrosion resistance nature of zinc-tin double-layer electroplating steel plate and same thickness is suitable even good slightly; Tin coating above the zinc-tin double-layer electroplating steel plate can improve the erosion resistance of steel plate on the one hand jointly with zinc coating, can guarantee again that on the other hand steel plate has the beautiful outward appearance and the product characteristics of asepsis environment-protecting.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
Sample adopts high-quality low-carbon cold rolling tole, specimen size: 120 * 120 * 0.18mm, and preparation process is following;
1) steel plate elder generation pickling, rust cleaning, wash at degreasing;
2) again steel plate being used weight percent is rare H of 10%
2SO
4Activation;
3) it is zinc-plated the steel plate after the activation to be sent into plating tank; Consisting of of this galvanizing solution: zinc sulfate (ZnSO
47H
2O): 475g/L, Tai-Ace S 150 (Al
2(SO
4)
318H
2O): 28g/L, sodium sulfate (Na
2SO
4): 52g/L, alum (KAl (SO
4)
212H
2O) 45g/L, pH value 3.8, temperature: room temperature, cathode current density: 3A/dm
2, zinc-plated amount: 2.8g/m
2
The surface of steel plate water that 4) will plate behind the zinc cleans up, put into immediately electroplate molten tin bath carry out zinc-plated, the consisting of of tin plating solution: stannous fluoboric acid (Sn (BF
4)
2) 190g/L, fluoroboric acid (dissociating) HBF
4150g/L, gelatin 6g/L, β-Nai Fen 0.9g/L, 25 ℃ of plating bath working temperatures, cathode current density 10A/dm
2, zinc-plated amount: 1.0g/m
2
The steel plate water that 5) will plate behind the tin cleans up; With resistance soft heat stove tin plate is carried out soft heat, hardening, soda cleaning, the passivation of chromic salt negative electrode then, the passivating solution composition is: sodium dichromate 99 25g/L, pH value 4～5; Solution temperature is 60 ℃, and electrochemistry negative electrode passivation electric weight is not less than 2.5C/dm
2During the passivation of electrochemistry negative electrode in the passive film chrome content be 8mg/m
2, the zinc-tin double-layer electroplating steel plate washing that passivation is finished, dry up and get product.
Embodiment 2
Sample adopts high-quality low-carbon cold rolling tole, specimen size: 120 * 120 * 0.25mm, and preparation process is following;
1) steel plate elder generation pickling, rust cleaning, wash at degreasing;
2) again steel plate being used weight percent is rare H of 15%
2SO
4Activation;
3) it is zinc-plated the steel plate after the activation to be sent into plating tank; Consisting of of this galvanizing solution: zinc sulfate (ZnSO
47H
2O): 490g/L, Tai-Ace S 150 (Al
2(SO
4)
318H
2O): 30g/L, sodium sulfate (Na
2SO
4): 48g/L, alum (KAl (SO
4)
212H
2O) 48g/L, pH value 4, temperature: room temperature, cathode current density: 2A/dm
2, zinc-plated amount: 1.5g/m
2
The surface of steel plate water that 4) will plate behind the zinc cleans up, put into immediately electroplate molten tin bath carry out zinc-plated, the consisting of of tin plating solution: stannous fluoboric acid (Sn (BF
4)
2) 200g/L, fluoroboric acid (dissociating) HBF
4120g/L, gelatin 5g/L, β-Nai Fen 1.0g/L, 30 ℃ of plating bath working temperatures, cathode current density 5A/dm
2, zinc-plated amount: 2.8g/m
2
The steel plate water that 5) will plate behind the tin cleans up; With resistance soft heat stove tin plate is carried out soft heat, hardening, soda cleaning, the passivation of chromic salt negative electrode then, the passivating solution composition is: sodium dichromate 99 20g/L, pH value 4～5; Solution temperature is 62 ℃, and electrochemistry negative electrode passivation electric weight is not less than 2.5C/dm
2During the passivation of electrochemistry negative electrode in the passive film chrome content be 5mg/m
2, the zinc-tin double-layer electroplating steel plate washing that passivation is finished, dry up and get product.
Embodiment 3
Sample adopts high-quality low-carbon cold rolling tole, specimen size: 120 * 120 * 0.35mm, and preparation process is following;
1) steel plate elder generation pickling, rust cleaning, wash at degreasing;
2) again steel plate being used weight percent is rare H of 12%
2SO
4Activation;
3) it is zinc-plated the steel plate after the activation to be sent into plating tank; Consisting of of this galvanizing solution: zinc sulfate (ZnSO
47H
2O): 480g/L, Tai-Ace S 150 (Al
2(SO
4)
318H
2O): 29g/L, sodium sulfate (Na
2SO
4): 49g/L, alum (KAl (SO
4)
212H
2O) 46g/L, pH value 4.3, temperature: room temperature, cathode current density: 1.5A/dm
2, zinc-plated amount: 4.0g/m
2
The surface of steel plate water that 4) will plate behind the zinc cleans up, put into immediately electroplate molten tin bath carry out zinc-plated, the consisting of of tin plating solution: stannous fluoboric acid (Sn (BF
4)
2) 195g/L, fluoroboric acid (dissociating) HBF
4180g/L, gelatin 5.5g/L, β-Nai Fen 1.1g/L, 35 ℃ of plating bath working temperatures, cathode current density 8A/dm
2, zinc-plated amount: 1.5g/m
2
The steel plate water that 5) will plate behind the tin cleans up; With resistance soft heat stove tin plate is carried out soft heat, hardening, soda cleaning, the passivation of chromic salt negative electrode then, the passivating solution composition is: sodium dichromate 99 23g/L, pH value 4～5; Solution temperature is 65 ℃, and electrochemistry negative electrode passivation electric weight is not less than 2.5C/dm
2During the passivation of electrochemistry negative electrode in the passive film chrome content be 7mg/m
2, the zinc-tin double-layer electroplating steel plate washing that passivation is finished, dry up and get product.
Embodiment 4
Sample adopts high-quality low-carbon cold rolling tole, specimen size: 120 * 120 * 0.50mm, and preparation process is following;
1) steel plate elder generation pickling, rust cleaning, wash at degreasing;
2) again steel plate being used weight percent is rare H of 14%
2SO
4Activation;
3) it is zinc-plated the steel plate after the activation to be sent into plating tank; Consisting of of this galvanizing solution: zinc sulfate (ZnSO
47H
2O): 495g/L, Tai-Ace S 150 (Al
2(SO
4)
318H
2O): 32g/L, sodium sulfate (Na
2SO
4): 50g/L, alum (KAl (SO
4)
212H
2O) 50g/L, pH value 3.9, temperature: room temperature, cathode current density: 1A/dm
2, zinc-plated amount: 5.6g/m
2
The surface of steel plate water that 4) will plate behind the zinc cleans up, put into immediately electroplate molten tin bath carry out zinc-plated, the consisting of of tin plating solution: stannous fluoboric acid (Sn (BF
4)
2) 210g/L, fluoroboric acid (dissociating) HBF
4200g/L, gelatin 6g/L, β-Nai Fen 1.0g/L, 28 ℃ of plating bath working temperatures, cathode current density 4A/dm
2, zinc-plated amount: 2.0g/m
2
The steel plate water that 5) will plate behind the tin cleans up; With resistance soft heat stove tin plate is carried out soft heat, hardening, soda cleaning, the passivation of chromic salt negative electrode then, the passivating solution composition is: sodium dichromate 99 24g/L, pH value 4～5; Solution temperature is 60 ℃, and electrochemistry negative electrode passivation electric weight is not less than 2.5C/dm
2During the passivation of electrochemistry negative electrode in the passive film chrome content be 6mg/m
2, the zinc-tin double-layer electroplating steel plate washing that passivation is finished, dry up and get product.
Embodiment 5: corrosion resistant test---salt spray corrosion test
In order to compare the corrosion resisting property of zinc-tin double-layer electroplating steel plate; Quickening the rotten solidity to corrosion of testing zinc-tin double-layer electroplating steel plate and pure tin plate through neutral salt spray compares; Because tin plate generally is to be used for food cans, beverages can, various assorted jar and bottle cap and the dried dress of various tin graphed sheet box etc.; And the tin layer that is plated is generally all thinner, and for this reason, the Low Concentration NaCl Solution of employing 1% is carried out the salt fog accelerated corrosion test to Coated Steel.Test-results is employed in the pure tin coating sample that is coated with same thickness on the steel plate and evaluates with the method that zinc-tin double-layer electroplating steel plate sample compares under identical etching condition.
The condition of salt-fog test is following:
NaCl strength of solution: 1%
Sample is put angle: 30
Salt fog cabinet controlled temperature: 36 ± 2 ℃
The thickness of zinc-tin double-layer electroplating steel plate does, earlier at surface of steel plate plating 2.8g/m
2Zinc plates 2.8g/m again on zinc coating
2Tin, the thickness of the double-deck coating of zinc-tin adds up to 5.6g/m like this
2Being used for correlated sample is that the surface is coated with 5.6g/m
2The Coated Steel of pure tin, two kinds of specimen surfaces all adopt chromic acid to carry out passivation, and the thickness of chromate passivation film is 6mg/m
2
Salt-fog test has been carried out 70 hours altogether, and test-results is seen table 1.
Table 1: salt-fog test result
Can find out that from the salt-fog test result zinc-tin double-layer electroplating steel plate of the present invention is after 70 hours salt-fog test, its salt spray corrosion resistance is better than pure tin Coated Steel.
Claims (7)
1. the method for manufacture of a zinc-tin double-layer electroplating steel plate, it is characterized in that: it may further comprise the steps:
1) the low-carbon cold rolling steel plate is carried out pickling, rust cleaning, degreasing, cleans and handle, and use diluted acid activation, said diluted acid to be weight percentage to be the dilute sulphuric acid of 10-15%;
2) steel plate after the activation is carried out electro-galvanizing, the consisting of of galvanizing solution: zinkosite is 475～495g/L, and Patent alum is 28～32g/L, and sodium sulfate is 48～52g/L, and alum is 45～50g/L, and the pH value is 3.8～4.3;
The surface of steel plate that 3) will plate behind the zinc washes, and carries out eleetrotinplate then, the consisting of of tin plating solution: stannous fluoboric acid is 190～210g/L, and free fluorine boric acid is 100～200g/L, and gelatin is 5～6g/L, and β-Nai Fen is 0.9～1.1g/L;
4) plated tin after water sample is cleaned up, with resistance soft heat stove tin plate is carried out then that soft heat, hardening, soda are cleaned, the passivation of chromic salt negative electrode, passivating solution consists of: sodium dichromate 99 is 20～25g/L, the pH value is 4～5;
5) the zinc-tin double-layer electroplating steel plate that passivation is finished is washed, is dried up, and gets product.
2. the method for manufacture of zinc-tin double-layer electroplating steel plate according to claim 1 is characterized in that: said step 2), the temperature of electro-galvanizing is a room temperature, and cathode current density is 1～3A/dm
2, in the said step 3), the temperature of eleetrotinplate is 25～35 ℃, cathode current density is 3～12A/dm
2
3. the method for manufacture of zinc-tin double-layer electroplating steel plate according to claim 1 and 2 is characterized in that: said step 2), the electro-galvanizing amount is 1.0～6.0g/m
2, in the said step 3), the eleetrotinplate amount is 1.0～6.0g/m
2
4. the method for manufacture of zinc-tin double-layer electroplating steel plate according to claim 1 and 2 is characterized in that: in the said step 4), passivation temperature is 60～65 ℃, and electrochemistry negative electrode passivation electric weight is 2.5C/dm
2
5. the method for manufacture of zinc-tin double-layer electroplating steel plate according to claim 3 is characterized in that: in the said step 4), passivation temperature is 60～65 ℃, and electrochemistry negative electrode passivation electric weight is not less than 2.5C/dm
2
6. the method for manufacture of zinc-tin double-layer electroplating steel plate according to claim 4 is characterized in that: in the said step 4), during the negative electrode passivation in the passive film chrome content be 5～8mg/m
2
7. the method for manufacture of zinc-tin double-layer electroplating steel plate according to claim 5 is characterized in that: in the said step 4), during the negative electrode passivation in the passive film chrome content be 5～8mg/m
2
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|---|---|---|---|
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|---|---|---|---|
| CN2011101155449A CN102206842B (en) | 2011-05-05 | 2011-05-05 | Manufacturing method of zinc/tin double-layer electroplated steel plate |
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| CN102206842B true CN102206842B (en) | 2012-10-31 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899692A (en) * | 2012-10-25 | 2013-01-30 | 中国科学院海洋研究所 | Method for preparing marine antifouling zinc coating solution |
| CN105018976A (en) * | 2014-04-21 | 2015-11-04 | 上海梅山钢铁股份有限公司 | Cold-rolled tin plate for tank used for containing protein food and manufacturing method of cold-rolled tin plate |
| CN104087982A (en) * | 2014-06-17 | 2014-10-08 | 宁国新博能电子有限公司 | Electrolyte |
| CN104195607A (en) * | 2014-08-29 | 2014-12-10 | 武汉钢铁(集团)公司 | Manufacturing method of tin-copper double-layer electroplated steel plates |
| CN104878421A (en) * | 2015-06-15 | 2015-09-02 | 武汉钢铁(集团)公司 | Manufacturing method of nickel/zinc cobalt alloy double-layer electroplated steel plate |
| CN104988456B (en) * | 2015-06-26 | 2017-08-25 | 武汉钢铁有限公司 | A kind of production method of the very thin steel band of the double composite deposites of Cu Sn/Sn Au |
| RU2606364C1 (en) * | 2015-10-15 | 2017-01-10 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Method of protective coating producing |
| CN106191937A (en) * | 2016-08-23 | 2016-12-07 | 合肥东方节能科技股份有限公司 | A kind of zinc-plated anti-corrosion treatment process of steel surface |
| CN107099831A (en) * | 2017-03-29 | 2017-08-29 | 首钢京唐钢铁联合有限责任公司 | A kind of manufacture method of the secondary cold-rolling tin plate of high sulfur resistive food cans |
| RU2718794C1 (en) * | 2019-10-30 | 2020-04-14 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Anticorrosive coating application method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365230A (en) * | 1976-11-25 | 1978-06-10 | Nippon Steel Corp | Zinc tin coated steel material |
| US4508601A (en) * | 1982-09-07 | 1985-04-02 | Toyo Kohan Co., Ltd. | Process for producing a thin tin and zinc plated steel sheet |
| CN101619474B (en) * | 2009-07-21 | 2010-09-01 | 武汉钢铁(集团)公司 | Manufacturing method of zinc-nickel double-layer electroplating steel plate |
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