CN102162110B - Methyl sulfonate tinning electrolyte and tinning method of steel strip or steel plate - Google Patents
Methyl sulfonate tinning electrolyte and tinning method of steel strip or steel plate Download PDFInfo
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- CN102162110B CN102162110B CN2011100330718A CN201110033071A CN102162110B CN 102162110 B CN102162110 B CN 102162110B CN 2011100330718 A CN2011100330718 A CN 2011100330718A CN 201110033071 A CN201110033071 A CN 201110033071A CN 102162110 B CN102162110 B CN 102162110B
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Abstract
The invention discloses methyl sulfonate tinning electrolyte using cerium salt as an additive. The electrolyte comprises the following components: 30 to 120 g/L of stannous methyl sulfonate, 60 to 180 g/L of methylsulfonic acid, 1 to 10 g/L of cerium sulfate, 0.1 to 2 g/L of antioxidant, 5 to 10 g/L of brightening agent and 5 to 10 g/L of surfactant. The invention also discloses a method for tinning a steel strip or a steel plate by adopting the electrolyte. During plating, the cerium salt in the electrolyte lightens the harm degree of 'hydrogen brittleness', and plays roles of the antioxidant and the brightening agent. On the basis of adaptability to the environment, the electrolyte meets the requirements that the process is simple, the solution is stable, the maintenance is easy and the quality of a coating is high.
Description
Technical field
The present invention relates to electrolytic solution and electro-plating method that the surface of light metal material is handled, refer more particularly to and a kind ofly be the metilsulfate tin plating electrolyte of additive and carry out electric plating method with this metilsulfate tin plating electrolyte with cerium salt.
Background technology
At present, tin plate is cold rolling Low Carbon Steel or the steel band that the two sides is coated with pure tin.It with solidity to corrosion, weldability and attractive in appearance the rolling into one of tin, has advantages such as nontoxic, that ductility good, solidity to corrosion is good with the intensity of steel and formability, and its surface is rich in gloss, the easy coloring printing.Therefore, tin plate is for a long time as the main wrapping material of foodstuffs industry, and is widely used in industries such as medicine, light industry, automobile and household electrical appliances, is one of most popular steel product.
All there is the shortcoming of high pollution (like fluoroborate, phenolsulfonate and halogenide etc.), plating bath unstable (vitriol) in the zinc-plated industry of traditional electrical.Methylsulphonic acid is claimed methylsulfonic acid or methanesulfonic again, is called for short MSA (Methane Sulfonic Acid), and structural formula is CH
3SO
3H is a kind of organic acid, non-oxidizing acid, is widely used as surface-treated leveling agent and brightening agent.Compare with the fluoroborate bath system with vitriol, the MSA bath system is stable in acidity, neutrality and basic soln.In addition, the MSA plating bath can be operated under very high current density, like high speed electrodeposition and continuous electroplating, can improve the solubility of tensio-active agent and other organic additive.The most important thing is that the MSA plating bath has remarkable advantages aspect environmental protection, its toxicity is lower than fluoroboric acid and silicofluoric acid; Can biological degradation, finally generate vitriol and carbonic acid gas, rate capable of circulation reaches 80%, therefore, the zinc-plated system of metilsulfate will become zinc-plated in most widely used technology.
The low oxidation rate of MSA plating bath requires to use some insoluble anodes to replace the used solubility tin anode of halogenation production line to keep the concentration of stannous ion in the plating bath, and current density should be higher than 10A/dm simultaneously
2For preventing Sn
2+Oxidation and hydrolytic precipitation cause the stability of solution to reduce, and free MSA should keep certain content in the plating bath.But too high levels can be dissolved by accelerating anode, makes Sn
2+Mass concentration further rises, and causes coating coarse, increases hydrogen-separating quantity simultaneously, causes electric current to descend; Content is low excessively, and bath stability is reduced, and current density range dwindles.But the key distinction of various MSA plating bath technologies is to comprise the different of additive types such as tensio-active agent, inhibitor, brightening agent and content, so the main still Study on Additive of the tinned research and development of metilsulfate.
People's such as Hu Lixin research document (is electroplated and environmental protection; 2009,29 the 6th phases of volume: 29-32) disclose a kind of methylsulphonic acid eleetrotinplate prescription: stannous methanesulfonate 8～10mL/L, methylsulphonic acid 96～112mL/L with good stability; Resorcinol 1.0～1.5g/L; 2-mercaptobenzimidazole (M) 0.2～0.3g/L, phenolphthalein 1.0～1.6mL/L, OP-10 tensio-active agent 1.0～1.4mL/L.But if temperature too high (>=35 ℃), plating bath stable bad, Sn
2+Be oxidized to Sn easily
4+, make electrolytic solution muddy, and coating is coarse, be difficult on the zinc-plated production line of hot conditions and use this method.Used the basal component of thionamic acid as electrolytic solution in the Russia SU1678094 patent documentation, sulphosalicylic acid and polyoxyethylene glycol sulfuric acid ester are as additive.But this processing parameter is strict, and especially the restriction of electroplating temperature makes this method should not be used for actual production.In addition, it is harmful to environment to contain sulphosalicylic acid in the electrolytic tinning liquid of this preparation, also makes this method be difficult to large-scale promotion and uses.Exploitation can reduce disadvantageous effect, the more excellent additive of performance will be the emphasis of the zinc-plated technology of current metilsulfate.
Turn usefulness into because the brightening agent in the metilsulfate tin plating electrolyte plays resistance to the electrodeposition process of tin, help obtaining careful, the bright coating of crystallization.Owing to constantly consume, when its content during, can not plate out the coating of light, and the resolvent of brightening agent and metallic impurity also can influence the performance of electrolytic solution less than certain value along with electroplating process.Novel brightening agent exploitation in the metilsulfate tin plating electrolyte is the research and development emphasis of the zinc-plated technology of metilsulfate always.
Rare earth has obtained extensive studies and application as electroplating additive.In vitriol and fluoroborate bath system, cerium salt not only can suppress Sn in the acid tank liquor
4+Generation, improved the stability of plating bath; Simultaneously can enlarge the cathode current density scope; Strengthen the covering power of plating bath, widen the bright range of coating, improve the solidity to corrosion of coating and the specific conductivity of coating (Xuan Tianpeng etc. " cerium is to the influence of tinned lead weldability ": " electroplating and finish "; 1993, the 15th volume the 5th phase: 11-13; Yu Jin etc. " cerium salt pair eleetrotinplate parameter and Effect on Performance ": sufacing,, the 33rd the 2nd phase of volume: 62-63) in 2004.In the metilsulfate tin plating electrolyte, do not see the report that adds rare-earth salts at present as yet.
Summary of the invention
Technical problem to be solved by this invention is: taken all factors into consideration on the basis of environmental protection, a kind of good stability is provided, and can improve the metilsulfate tin plating electrolyte of luminance brightness, corrosion resisting property and the welding property of tin coating.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is: a kind of metilsulfate tin plating electrolyte comprises following composition (g/L): 30～120 stannous methanesulfonates, 60～180 methylsulphonic acids; 1～10 cerous sulfate; 0.1～2 inhibitors, 5～10 brightening agents and 5～15 tensio-active agents, described inhibitor are Resorcino or catechol or both mixtures; Described brightening agent is LUTARALDEHYDE or benzylidene-acetone or both mixtures, and described tensio-active agent is polyoxyethylene octyl phenyl ether or sodium laurylsulfonate or both mixtures.
Another technical problem to be solved by this invention is: a kind of steel band of luminance brightness, corrosion resisting property and the welding property that improves tin coating or the tin plating method of steel plate are provided.
The technical scheme that the present invention adopts is: the tin plating method of steel band or steel plate has adopted above-mentioned metilsulfate tin plating electrolyte.During plating, the transfer rate of steel band or steel plate is 3～9m/s, and plating temperature is 15～60 ℃, and current density is 6～20A/dm
2
Before plating, steel band or steel plate are carried out degreasing and pickling pre-treatment.
Steel band after the plating or steel plate are carried out soft heat, passivation and tin layer oiling aftertreatment.
The invention has the beneficial effects as follows: contain cerium salt in the electrolytic solution described in the present invention, enlarged the cathode current density scope, strengthen the covering power of plating bath, widen the bright range of coating, improve the solidity to corrosion of coating and the specific conductivity of coating; Brightening agent in this electrolytic solution plays resistance to the electrodeposition process of tin and turns usefulness into; Help obtaining careful, the bright coating of crystallization; And cerium is easy to be adsorbed on the active site of crystal growth; Can effectively suppress crystal growth, make the coating grain refining and surface-brightening is careful, reduce the consumption of the brightening agent in the metilsulfate tin plating electrolyte; Simultaneously, cerium is stronger to the magnetism of electronics, and rare earth forms ion easily in solution, and the specific adsorption of cerium ion makes hydrogen ion stop hydrionic selectivity in raising of negative electrode deposition potential and adsorption film, has alleviated the hazard rating of " hydrogen embrittlement "; Cerous sulfate suppresses Sn as inhibitor in the above-mentioned electrolytic solution
2+Change into Sn
4+, improved the stability of plating bath.
Metilsulfate tin plating electrolyte of the present invention is placed experiment, heated constant temperature oxidation style and H
2O
2The bath stability performance of promote the oxidation experiment is tested, and coating has been carried out binding force of cladding material detection, the detection of high temperature resistance oxidation-resistance, the anti-sulphur corrosion ability experiment of coating and weldability test experience.Experiment proof cerous sulfate additive has improved electrolytic solution stability, has increased the covering power of electrolytic solution, has improved luminance brightness, corrosion resisting property and the welding property of tin coating simultaneously.
Embodiment
Describe the present invention below in conjunction with specific embodiment.
Embodiment 1:
At first; The preplating sample is carried out pre-washing and pickling (according to " Ferrostan (Fei Luositan) " method) pre-treatment; It is zinc-plated that sample after the processing carries out metilsulfate by following condition, and zinc-plated back sample carries out soft heat, Passivation Treatment and tin layer oiling aftertreatment.20 ℃ of electroplating temperatures, current density 6A/dm
2, the speed of negative electrode travelling belt is 3m/s.During electrolyte quota; Clean up coating bath with tap water and deionized water respectively; Then; The deionized water that adds 1/2 volume adds methylsulphonic acid, the inferior tin of methylsulfonic acid, cerous sulfate, Resorcinol, catechol, benzylidene-acetone, LUTARALDEHYDE, OP-10, sodium laurylsulfonate successively by calculated amount; Then, adding deionized water to prescribed volume, is electrodepositable after stirring.The prescription of electrolytic solution is following:
Embodiment 2:
25 ℃ of electroplating temperatures, current density 8A/dm
2, the speed of negative electrode travelling belt is 3m/s, other are identical with embodiment 1.The prescription of electrolytic solution is following:
Embodiment 3
30 ℃ of electroplating temperatures, current density 10A/dm
2, the speed of negative electrode travelling belt is 3m/s, other are identical with embodiment 1.The prescription of electrolytic solution is following:
Embodiment 4
40 ℃ of electroplating temperatures, current density 12A/dm
2, the speed of negative electrode travelling belt is 6m/s, other are identical with embodiment 1.The prescription of electrolytic solution is following:
Embodiment 5
50 ℃ of electroplating temperatures, current density 15A/dm
2, the speed of negative electrode travelling belt is 6m/s, other are identical with embodiment 1.The prescription of electrolytic solution is following:
Embodiment 6
55 ℃ of electroplating temperatures, current density 20A/dm
2, the speed of negative electrode travelling belt is 9m/s, other are with real
It is identical to execute example 1.The prescription of electrolytic solution is following:
For the eleetrotinplate solution that confirms this preparation possesses good stability, carry out following experiment:
Place experiment: get following each 1L of the test solution for preparing, under 20 ℃ temperature, keep the tin anode plate and place test, with the examination bath stability.The result is as shown in table 1 for the experiment gained.
The heated constant temperature oxidation style: below each 50ml of test solution of preparing; Contain respectively in what open wide and have in the graduated small beaker; Place temperature to be controlled at 50 ± 5 ℃ thermostat(t)ed water, under the condition of astigmatism irradiation, observe test solution and become muddy degree; The record test solution begins to become muddy and complete muddy required time, and analyzes respectively with iodimetry,iodometry and to join test solution, test solution Sn in the solution when beginning to become muddy and complete muddiness at present
2+Content.The result is as shown in table 2 for the experiment gained.
H
20
2Promote the oxidation experiment: get following each 50ml of the test solution for preparing, contain respectively in 100ml and have in the graduated beaker, each drips 20 ydrogen peroxide 50, observe phenomena, and drip H with iodimetric analysis
2O
2Sn in the solution of front and back
2+Content.The result is as shown in table 3 for the experiment gained.
Table 1: the test result of placing experiment
Table 2: the test result of heated constant temperature oxidation
Table 3:H
2O
2The promote the oxidation experimental result
Phenomenons such as binding force of cladding material detects: the coating that obtains according to foregoing invention carries out crooked test, and coating do not have bubble, come off; Carry out cut, coating does not all have peeling, explains that binding force of cladding material is good.
The high temperature resistance oxidation-resistance detects and electroplates resulting eleetrotinplate alloy components to electrolytic tinning liquid of the present invention, rack plating and barrel plating person, and through repeatedly toasting 2 hours down at 200 ± 5 ℃, coating surface all keeps original gloss, and non-foaming decortication.Repeatedly in 100 ℃ steam, tested 1 hour the equal no change of coating surface, non-foaming decortication.
Claims (5)
1. metilsulfate tin plating electrolyte; Comprise following composition: 30～120g/L stannous methanesulfonate; 60～180g/L methylsulphonic acid, 1～10g/L cerous sulfate, 0.1～2g/L inhibitor; 5～10g/L brightening agent and 5～15g/L tensio-active agent; Described inhibitor is Resorcino or catechol or both mixtures, and described brightening agent is LUTARALDEHYDE or benzylidene-acetone or both mixtures, and described tensio-active agent is polyoxyethylene octyl phenyl ether or sodium laurylsulfonate or both mixtures.
2. the tin plating method of steel band or steel plate is characterized in that: adopted metilsulfate tin plating electrolyte as claimed in claim 1.
3. the tin plating method described in claim 2, it is characterized in that: during plating, the transfer rate of steel band or steel plate is 3～9m/s, and plating temperature is 15～60 ℃, and current density is 6～20A/dm
2
4. the tin plating method described in claim 2 is characterized in that: before plating, steel band or steel plate are carried out degreasing and pickling pre-treatment.
5. the tin plating method described in claim 2 is characterized in that: steel band after the plating or steel plate are carried out soft heat, passivation and tin layer oiling aftertreatment.
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| CN102605392A (en) * | 2012-04-18 | 2012-07-25 | 吉安市荣泰电讯科技有限公司 | Tin plating liquid with rear earth additive |
| CN103014786B (en) * | 2013-01-22 | 2016-01-20 | 广州博泉环保材料科技有限公司 | Electroplate liquid, its preparation method and apply the tin plating technique of this electroplate liquid |
| CN104087984A (en) * | 2014-06-17 | 2014-10-08 | 宁国新博能电子有限公司 | Tinning electrolyte of tinned copper wire for electronic component lead wires |
| CN104099649B (en) * | 2014-06-25 | 2016-08-24 | 武汉钢铁(集团)公司 | Passivator for electrolytic tinplate |
| CN104060308B (en) * | 2014-06-30 | 2016-09-14 | 句容市博远电子有限公司 | A kind of Pure Tin Plating Process liquid reducing dew copper phenomenon and application thereof |
| CN104988544A (en) * | 2015-06-26 | 2015-10-21 | 吕小方 | Electrolytic tinning annexing agent |
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| CN109596681B (en) * | 2017-09-30 | 2021-07-09 | 上海梅山钢铁股份有限公司 | Method for detecting uniform plating capacity of tin methanesulfonate electroplating solution |
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| CN111647917A (en) * | 2020-05-22 | 2020-09-11 | 成都宏明双新科技股份有限公司 | Process for preventing tin-plated product from discoloring in high-temperature test |
| CN113957495A (en) * | 2020-07-21 | 2022-01-21 | 宝山钢铁股份有限公司 | Brightener for PSA (pressure swing adsorption) electrotinning insoluble anode system and application |
| CN112111763A (en) * | 2020-09-30 | 2020-12-22 | 首钢集团有限公司 | Preparation method of tin plate with high tin plating amount and product thereof |
| CN114507813A (en) * | 2020-11-17 | 2022-05-17 | 上海梅山钢铁股份有限公司 | Ultralow tin-plating layer cold-rolled electroplated tin steel plate and manufacturing method thereof |
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