CN115961317A - Electrotinning steel plate and manufacturing method thereof - Google Patents
Electrotinning steel plate and manufacturing method thereof Download PDFInfo
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- CN115961317A CN115961317A CN202111184833.4A CN202111184833A CN115961317A CN 115961317 A CN115961317 A CN 115961317A CN 202111184833 A CN202111184833 A CN 202111184833A CN 115961317 A CN115961317 A CN 115961317A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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Abstract
The invention discloses an electrotinning steel plate, which comprises a steel substrate and a tinning layer, wherein the tinning layer comprises a pure tin layer and a tin-iron alloy transition layer positioned between the pure tin layer and the steel substrate, the surface of the tinning layer is covered with a passive film, and the passive film contains 3.5-36 mg/m 2 The chromium content includes a metallic chromium content and a chromium oxide content. In addition, the invention also discloses a passivation solution for forming a passivation film on the surface of the electrotinning steel plate, wherein the solvent of the passivation solution is water, and the passivation solution contains: chromic anhydride with the concentration of 20-180 g/L; an additive selected from: 0.2 to 0.8g/L sulfuric acid, 0.5 to 3.5g/L sodium sulfate, 0.8 to 2.5g/L fluosilicic acid or 1.5 to 6.5g/L sodium fluosilicate. Correspondingly, the invention also discloses a manufacturing method of the electrotinning steel plate, which can be used for manufacturing the electrotinning steel plate.
Description
Technical Field
The invention relates to a composite material and a manufacturing method thereof, in particular to a tin plate and a manufacturing method thereof.
Background
As is well known, the electroplated tin steel plate is a product with complex production technology, long manufacturing process, high quality requirement and great manufacturing difficulty, and is generally prepared by plating a layer of pure tin on both sides of a cold-rolled low-carbon steel sheet.
In the prior art, because tin in the electroplated tin steel plate has no toxicity, and the steel plate has the characteristics of higher strength, good formability, excellent corrosion resistance, stronger weldability and good printing colorability, users generally use the electroplated tin steel plate in the field of food or beverage packaging which needs to be subjected to high-temperature stewing and sterilizing processing, such as the manufacture of metal food cans or beverage cans.
In the process of producing the tin-plated steel plate, the selected steel substrate generally needs to be subjected to pretreatment, tin-plating treatment and reflow treatment to obtain the tin-plated steel plate; after the above process is completed, the tin-plated steel sheet may form a tin-plated layer, and the formed tin-plated layer may include a tin-iron alloy transition layer and a pure tin layer.
Because tin is easily oxidized in the air, in order to ensure that the tin-electroplated steel plate has good service performance, the surface of the tin-electroplated steel plate is generally required to be further passivated to form a functional protective layer, namely a passivation film; the corrosion resistance and the blackening resistance of the electrotinning steel plate can be effectively improved by passivating the electrotinning steel plate, and the electrotinning steel plate is endowed with good finishing performance.
At present, the traditional passivation method of the electrotinning steel plate adopts a production process of carrying out electrolytic treatment on a dichromate solutionThe chromium in the tin-plated steel plate can be reduced into trivalent chromium oxide or metallic chromium by electrolysis, and is deposited on the surface of a tin layer of the tin-plated steel plate by a basic passivation process: the composition of the passivation solution is 25 +/-5 g/L sodium dichromate (H) 2 Cr 2 O 7 ) The temperature of the passivation solution is 42 +/-5 ℃, the pH value is 4 +/-1, the passivation time is about 1s, and the passivation electric quantity is 3C/dm 2 。
Although the tin-plated steel treated by the surface treatment method can meet the requirements of various aspects, with the development of printing equipment and technology, can making equipment and technology and the diversification of can contents, more and more application occasions need high coating adhesion and high sulfur resistance, and the prior passivation treatment technology of the tin-plated steel plate taking sodium dichromate as a main salt is difficult to meet the requirements of high coating adhesion and high sulfur resistance at the same time.
For the above reasons, the present invention is expected to develop a novel passivation solution that can be applied to the surface of a tin-plated steel sheet to perform a special surface treatment of the tin-plated steel sheet by the passivation solution, thereby obtaining a novel tin-plated steel sheet having good film adhesion and sulfur resistance.
The electrotinning steel plate prepared by the method has good coating adhesion and sulfur resistance, and the preparation method has the advantages of simple process, environment-friendly product, low application cost, good popularization prospect and good application value.
Disclosure of Invention
One of the purposes of the invention is to provide an electrotinning steel plate, which adopts special surface passivation treatment, and can cover a layer of passivation film on the surface of a self-tinning layer after the passivation treatment, thereby greatly improving the surface performance of the electrotinning steel plate and ensuring that the electrotinning steel plate obtains more excellent film adhesion and sulfur resistance.
The electroplated tin steel plate has excellent coating adhesion and sulfur resistance, can be effectively applied to the field of food or beverage packaging, and has good popularization prospect and application value.
In order to achieve the above object, the present invention provides an electrolytic tin-plated steel sheet comprising a steel substrate andthe tin coating comprises a pure tin layer and a tin-iron alloy transition layer positioned between the pure tin layer and a steel substrate, wherein the surface of the tin coating is covered with a passive film, and the passive film contains 3.5-36 mg/m 2 The chromium content includes a metallic chromium content and a chromium oxide content.
In the above technical solution of the present invention, the tin electroplated steel sheet of the present invention may include: a steel substrate and a tin-plated layer. Wherein, the steel substrate can be cold-rolled carbon steel sheet strip; the tin-plated layer may include a pure tin layer and a tin-iron alloy transition layer between the pure tin layer and the steel substrate.
In the present invention, the surface-passivated tin-electroplated steel sheet is further coated with a passivation film covering the surface of the tin-plated layer and containing 3.5 to 36mg/m 2 The chromium content comprises metal chromium content and chromium oxide content, and further, the content of the metal chromium in the passive film is 1.0-16 mg/m 2 。
The surface of the electrotinning steel plate is covered with a layer of passive film, and the electrotinning steel plate has good coating adhesion and sulfur resistance, can be effectively applied to the field of food or beverage packaging, and has good popularization prospect and application value.
Further, in the tin-plated steel sheet according to the present invention, the tin plating amount on one surface of the tin-plated steel sheet is 0.3 to 16g/m 2 。
Further, another object of the present invention is to provide a passivation treatment solution which can surface-treat an electrotinning steel sheet to form a passive film on the surface of the electrotinning steel sheet, the formed passive film having good surface stability properties and being capable of optimizing the coating adhesion and sulfur resistance of the electrotinning steel sheet.
In order to achieve the above object, the present invention provides a passivation solution for forming a passivation film on a surface of an electrotinning steel sheet according to the present invention, the passivation solution having water as a solvent, the passivation solution comprising:
chromic anhydride with the concentration of 20-180 g/L;
an additive selected from: 0.2 to 0.8g/L sulfuric acid, 0.5 to 3.5g/L sodium sulfate, 0.8 to 2.5g/L fluosilicic acid or 1.5 to 6.5g/L sodium fluosilicate.
In the technical scheme of the invention, the inventor creatively designs a novel passivation treatment solution, and the passivation treatment solution can be used for carrying out surface treatment on the tin-plated steel plate so as to form a passivation film on the surface of the tin-plated steel plate.
The passivation film formed by the surface treatment of the electrotinning steel plate by adopting the passivation treatment solution has good surface stability, and can effectively optimize the coating adhesion and the sulfur resistance of the electrotinning steel plate.
Further, in the passivation treating solution of the present invention, in the passivation treating solution:
the concentration of chromic anhydride is 20-80 g/L, and the additive is 0.2-0.8 g/L sulfuric acid; or alternatively
The concentration of chromic anhydride is 55-125 g/L, and the additive is 0.5-3.5 g/L sodium sulfate; or
The concentration of chromic anhydride is 75-150 g/L, and the additive is 0.8-2.5 g/L fluosilicic acid; or
The concentration of chromic anhydride is 75-180 g/L, and the additive is 1.5-6.5 g/L sodium fluosilicate.
Accordingly, it is still another object of the present invention to provide a method for manufacturing the above-described tin-electroplated steel sheet, which is simple and environmentally friendly, and by which the above-described tin-electroplated steel sheet of the present invention can be efficiently manufactured.
In order to achieve the above object, the present invention provides a method for manufacturing an electrotinning steel sheet, comprising the steps of:
(1) Carrying out electrotinning treatment on the steel substrate to form a tinned layer;
(2) Carrying out reflow treatment on the tin-plated steel plate;
(3) Sequentially carrying out surface treatment on the tin-plated steel plate according to the following steps to form the passive film on the surface of the tin-plated steel plate:
(a) Adopting a passivation treatment solution to pre-soak the tin-plated steel plate;
(b) Carrying out cathode electrolysis treatment on the tin-plated steel plate by adopting a passivation treatment solution;
(c) Adopting a passivation treatment solution to dip the tin-plated steel plate again;
wherein the solvent of the passivation solution is water, and the passivation solution contains: chromic anhydride with the concentration of 20-180 g/L; an additive selected from: sulfuric acid with the concentration of 0.2-0.8 g/L, or sodium sulfate with the concentration of 0.5-3.5 g/L, or fluosilicic acid with the concentration of 0.8-2.5 g/L, or sodium fluosilicate with the concentration of 1.5-6.5 g/L;
(4) Rinsing and oiling.
In the method for manufacturing the tin-electroplated steel plate, the steel substrate in the step (1) can be a cold-rolled carbon steel sheet strip generally; the cold-rolled carbon steel sheet strip used is usually subjected to cold rolling and annealing treatment, and some of the cold-rolled carbon steel sheet strip is subjected to secondary cold rolling after the annealing treatment is completed.
In the step (1), the steel substrate can be subjected to conventional electrotinning after necessary alkali washing and acid washing, the main salt of the electroplating solution adopted in the electrotinning can be selected from tin methane sulfonate (MSA electrotinning system) or tin phenol sulfonate (PSA electrotinning system), and necessary electroplating additives are contained, and the single-side tinning amount of the tinned steel plate can be controlled to be 0.3-16 g/m in the electrotinning process 2 。
After the tin electroplating treatment, the tin-plated steel sheet may be further subjected to a reflow treatment in step (2) to form a tin-iron alloy transition layer. The reflow treatment process can adopt resistance reflow or induction reflow independently, and can also adopt a combined reflow mode of resistance reflow and induction reflow.
Accordingly, after the reflow process of step (2) is completed, the surface treatment of the tin-plated steel sheet may be further performed in step (3) to perform a passivation process in a passivation treatment solution to form a passivation film on the surface of the tin-plated steel sheet.
In the method for producing a tin-plated steel sheet according to the present invention, in step (3), a desired cathodic electrolytic passivation film can be formed on the surface of the tin-plated steel sheet by performing a treatment method of a preliminary immersion treatment, a cathodic electrolytic treatment, and a chemical immersion treatment on the tin-plated steel sheet using a passivation solution. Wherein the treatment time of the pre-impregnation can be preferably controlled to be 1 to 5 times the cathodic electrolysis treatment time; the treatment time for the impregnation is preferably controlled to be 2 to 9 times the treatment time for the cathodic electrolysis.
Of course, in step (3), the use temperature of the passivation treatment solution may preferably be controlled to be 32 ℃ to 65 ℃.
Accordingly, in the above-mentioned step (3) of the production method of the present invention, the current density of the cathodic electrolysis treatment can be preferably controlled to be 20A/dm 2 ～100A/dm 2 (ii) a The anode plate material adopted by the cathode electrolysis treatment can be plain carbon steel or inert materials such as lead-tin alloy, platinum, iridium oxide and the like.
Further, in the manufacturing method of the present invention, in the passivation treatment solution:
the concentration of chromic anhydride is 20-80 g/L, and the additive is 0.2-0.8 g/L sulfuric acid; or alternatively
The concentration of chromic anhydride is 55-125 g/L, and the additive is 0.5-3.5 g/L sodium sulfate; or alternatively
The concentration of chromic anhydride is 75-150 g/L, and the additive is 0.8-2.5 g/L fluosilicic acid; or
The concentration of chromic anhydride is 75-180 g/L, and the additive is 1.5-6.5 g/L sodium fluosilicate.
Further, in the manufacturing method of the present invention, in the step (2), the tin-plated steel sheet is reflowed by resistance reflow and/or induction reflow.
Further, in the manufacturing method of the present invention, in the step (3), the treatment time of the pre-impregnation is 1 to 5 times the treatment time of the cathodic electrolysis; the treatment time of the impregnation in the step (c) is 2 to 9 times of the cathodic electrolysis treatment time.
Further, in the production method of the present invention, in the step (3), the cathodic electrolysis treatment time is 0.05 to 0.3s.
In the step (3), the time for performing the cathodic electrolysis treatment on the tin-plated steel sheet using the passivation treatment solution is determined according to the amount of the surface treatment layer required for the tin-plated steel sheet, and may be 0.05 to 0.3 seconds.
Further, in the production method of the present invention, in the step (3), the current density of the cathodic electrolysis treatment is 20A/dm 2 ～100A/dm 2 。
Further, in the manufacturing method of the present invention, the temperature of the passivation solution is 32 to 65 ℃.
Further, in the manufacturing method of the present invention, in the step (4), the oil is applied by electrostatic oil application, and the amount of the applied oil is controlled to be 1.5mg/m 2 ～9.5mg/m 2 。
In the above technical scheme of the present invention, in the step (4), the tin-plated steel plate subjected to the surface passivation treatment needs to be rinsed, either by immersion rinsing or spray rinsing; then, the drying can be carried out by selecting the treatment modes such as hot air drying, steam blowing and the like.
After rinsing and drying, the tinned steel plate can be oiled, generally adopting an electrostatic oiling mode, and the oiling amount can be controlled to be 1.5mg/m 2 ～9.5mg/m 2 。
Compared with the prior art, the electrotinning steel plate and the manufacturing method thereof have the advantages and beneficial effects as follows:
the inventors have creatively designed a new passivation treatment solution with which a tin-plated steel sheet can be surface-treated to form a passivation film on the surface of the tin-plated steel sheet. The passivation film has good surface stability, and the surface tin oxide does not grow significantly even after long-term storage or hot air baking during processing.
By using the above passivation treatment solution, the present invention can obtain a novel tin-plated steel sheet having a tin-plated layer surface covered with a passivation film, which has good corrosion resistance, blackening resistance and acid resistance.
Correspondingly, the paint film adhesion performance of the coated electrotinning steel plate is excellent, the manufacturing method is simple in process, the product is environment-friendly and low in application cost, heavy metal and organic matter components with potential toxicity to human bodies are not contained, food contact is non-toxic, the electrotinning steel plate is environment-friendly, and the electrotinning steel plate can be widely applied to the fields of food, beverages, chemical tanks and covers, electronic devices and the like, and has good popularization prospect and application value.
Drawings
Fig. 1 schematically shows a schematic view of an interlayer structure of an electrolytic tin-plated steel sheet according to the present invention.
Fig. 2 schematically shows an X photoelectron spectrum of a passivation film layer depth distribution of the tin-electroplated steel sheet of example 4.
Fig. 3 schematically shows an X photoelectron spectrum of the passivation film layer depth distribution of the tin-electroplated steel sheet of comparative example 2.
Detailed Description
The tin-electroplated steel sheet and the manufacturing method thereof according to the present invention will be further explained and illustrated with reference to the specific examples and the drawings of the specification, however, the explanation and illustration should not be construed as unduly limiting the technical solution of the present invention.
Examples 1 to 14
Table 1 shows the concentration ratios of the components in the passivation solutions of examples 1-14.
Table 1.
As shown in Table 1, the concentration ratios of the components in the passivation solutions of examples 1-14 of the present invention meet the preferred design control requirements of the present invention. In the present invention, the surface treatment of the tin-plated steel sheet using the passivation solution according to examples 1 to 14 of the present invention can form a passivation film on the surface of the tin-plated steel sheet.
In the present invention, a tin-plated steel sheet can be produced by performing an electrolytic tin plating treatment on a steel substrate selected from those in the prior art to form a tin-plated layer; the tin plating layer may include: a pure tin layer and a tin-iron alloy transition layer positioned between the pure tin layer and the steel substrate. Thus, the interlayer structure of the tin-plated steel sheet may sequentially include: steel substrate, tin-iron alloy transition layer, pure tin layer.
In the present invention, after the tin-plated steel sheet is surface-treated with the passivation solution according to examples 1 to 14 of the present invention, a passivation film may be formed on the surface of the tin-plated steel sheet, and the passivation film may be coated on the surface of the tin-plated layer, thereby obtaining the tin-plated steel sheet according to examples 1 to 14 of the present invention.
The chemical element components of the steel substrate of the tin-plated steel sheet are not particularly limited in the present invention, and it is only necessary to control the single-side tin plating amount of the tin-plated steel sheet to 0.3 to 16g/m 2 The component systems of the prior art which can achieve the technical effects of the scheme can be adopted. In the present invention, the steel substrates of the tin-plated steel sheets used in examples 1 to 14 were the same steel.
In the present invention, the electrotinning steel sheets of examples 1 to 14 were each produced by the following steps:
(1) Carrying out electrotinning treatment on the steel substrate to form a tinned layer: the steel substrate after cold rolling and annealing and tempering treatment is subjected to alkali cleaning degreasing and acid cleaning to activate the surface, then electrotinning treatment is carried out in electrotinning solution taking tin methane sulfonate as main salt, and the single-side tinning amount of the tinned steel plate is controlled to be 0.3-16 g/m 2 To form a tin-plated layer.
(2) Carrying out reflow treatment on the tin-plated steel plate: and performing reflow treatment on the tin-plated steel plate by adopting a resistance reflow and/or induction reflow mode.
(3) Sequentially carrying out surface treatment on the tin-plated steel plate according to the following steps to form the passive film on the surface of the tin-plated steel plate:
(a) Adopting a passivation treatment solution to pre-soak the tin plate;
(b) Carrying out cathode electrolysis treatment on the tin plate by adopting a passivation treatment solution;
(c) Adopting a passivation treatment solution to dip the tin plate again;
wherein the use temperature of the passivating treatment solution is controlled to be 32-65 ℃, the cathode electrolysis treatment time is controlled to be 0.05-0.3 s, and the current density of the cathode electrolysis treatment is controlled to be 20A/dm 2 ～100A/dm 2 The treatment time for the pre-dipping is controlled to be 1 to 5 times the treatment time for the cathodic electrolysis, and the treatment time for the re-dipping is controlled to be 2 to 9 times the treatment time for the cathodic electrolysis.
(4) Rinsing and oiling: after passivation treatment, necessary rinsing and drying are carried out, and then the oil is coated by adopting an electrostatic oil coating mode, wherein the oil coating amount is controlled to be 1.5mg/m 2 ～9.5mg/m 2 In the meantime.
Table 2 shows the relevant process parameters of the tin-electroplated steel sheets of examples 1 to 14 in the above-mentioned steps.
Table 2.
Accordingly, in order to show the superior performance of the tin-electroplated steel sheets of examples 1-14 according to the present invention, two conventional tin-electroplated steel sheets were further used in the present invention for comparison of performance as comparative example 1 and comparative example 2, respectively, it should be noted that comparative examples 1 and 2 were not treated with the passivation solution described in the present application.
The tin-electroplated steel sheets of the finished examples 1-14 and the tin-electroplated steel sheets of the comparative examples 1-2, which were finally prepared by the above-mentioned process of the present invention, were sampled, and the passive films of the tin-electroplated steel sheets of the examples 1-14 and the comparative examples 1-2 were tested, and the amount of metallic chromium, the amount of chromium oxide and the amount of total chromium of the passive films of the examples and the comparative examples were tested by the X-ray fluorescence method, and the relevant test results are listed in the following table 3.
Table 3 lists the total chromium content, metallic chromium content and chromium oxide content in the passive films of the tin-electroplated steel sheets of examples 1-14 and comparative examples 1-2.
Table 3.
Accordingly, after the above-described inspection of the passive film with respect to the tin-electroplated steel sheets of examples 1 to 14 and comparative examples 1 to 2 is completed, the tin-electroplated steel sheets of examples 1 to 14 and comparative examples 1 to 2 may be sampled again, and further inspection tests may be performed based on the sampled steel sheets.
In the present invention, a conventional epoxy novolac paint may be applied to the surfaces of the sample steel sheets of examples 1 to 14 and comparative examples 1 to 2 by blade coating, and the film thickness is controlled to be 7.0g/m 2 ～8.0g/m 2 The coating film is baked and cured for 12 minutes at 185 ℃ and then for 12 minutes at 205 ℃. After the sample steel sheets of examples 1 to 14 and comparative examples 1 to 2 were completely cooled, the coating adhesion and sulfur resistance properties thereof were evaluated, and the results of the evaluation of the coating adhesion and sulfur resistance properties thereof are shown in the following Table 4.
The adhesion evaluation method comprises the following steps: and marking a thread line with the length of 60-80 mm and the diameter of 10mm on a marking instrument with the thread pitch of 1.5mm at the speed of 90-100 r/min. The depth of the score line is to a degree to just penetrate the coating film. The scraped coating scraps are lightly brushed by a brush pen, a 3M610 adhesive tape is adhered to the threaded line, and the adhesive tape is tightly pressed to be completely adhered to the coating. Then, the coating film pattern was fixed, the adhesive tape was rapidly peeled from the coating film in an obliquely upward direction, and the areas of the coating film peeled from the tin-electroplated steel sheets of examples 1 to 14 and comparative examples 1 to 2 were observed.
Evaluation method of Sulfur resistance: evaluation of Sulfur resistance Properties the L-cysteine hydrochloride (C) was used as the solution 3 H 8 NO 2 SCl) 0.50g or L-form cysteine hydrochloride (C) 3 H 8 NO 2 SCl·H 2 O) 0.56g, potassium dihydrogen phosphate (KH) 2 PO 4 ) 3.60g disodium hydrogen phosphate dodecahydrate (Na) 2 HPO 4 ·12H 2 O) 18g, each dissolved in water, mixed and diluted to 1000mL. The specific evaluation method comprises the steps of continuously bending and folding the electroplated tin plate sample in parallel with the width direction of 30mm into a plurality of blocks with the length of 20 mm-30 mm, and pressing each folding surface to ensure that the bending part forms an included angle of about 180 degrees. When folded, it should be ensuredThe surface to be measured is folded to the outer bending surface. The prepared sample was immersed in a pressure-resistant vessel filled with the sulfur-resistant test solution, and the vessel was capped and sealed. The distance between the liquid level of the reagent for experiment and the inner surface of the cover of the container is ensured to be 5 mm-7 mm. The vessel was placed in a pressure steam sterilizer and cooked at 121 ℃ for 60 minutes. After natural cooling, the steel sheet was washed clean with industrial pure water, the surface was blown dry with cold air, and the blackening (i.e., the spots of vulcanization) of the surface of the tin-electroplated steel sheets of examples 1 to 14 and comparative examples 1 to 2 was observed.
Table 4 shows the results of the evaluation of the properties of the tin-electroplated steel sheets of examples 1 to 14 and comparative examples 1 to 2.
Table 4.
Note: in Table 4 above, gamma indicates poor response; "Δ" indicates the corresponding property is normal; "O" indicates better correspondence; "very good" means the corresponding performance is very good.
As can be seen from tables 3 and 4 of the present invention, in examples 1 to 6, the passivation solution and the corresponding passivation process designed according to the present invention were used, and the surface passivation treatment was performed to obtain the tin-electroplated steel sheets of examples 1 to 6, which were further coated with a passivation film covering the surface of the tin-plated layer, and which contained 3.5 to 36mg/m 2 The chromium content comprises metal chromium content and chromium oxide content, and the metal chromium content in the passive film is 1.0-16 mg/m 2 . The obtained tin-plated steel plate has good paint film adhesive force and good sulfur resistance.
Different from examples 1 to 14, the electrotinning steel plates of comparative examples 1 to 2 have better sulfur resistance when the amount of the passive film is higher, but the paint film adhesion is general; when the amount of the passive film is lower, the paint film has better adhesive force, but the sulfur resistance is poorer.
Fig. 1 schematically shows a schematic view of an interlayer structure of an electrolytic tin-plated steel sheet according to the present invention.
As shown in fig. 1, in the tin-electroplated steel sheet according to the present invention, the interlayer structure of the tin-electroplated steel sheet according to the present invention may include: the tin-iron alloy steel comprises a steel substrate 1, a tin-iron alloy transition layer 2, a pure tin layer 3, a passive film 4 and an oil layer 5. Wherein, the passivation film 4 covers the surface of the pure tin layer 3, and the passivation film 4 contains chromium and its oxide.
Fig. 2 schematically shows an X photoelectron spectrum of a passivation film layer depth distribution of the tin-electroplated steel sheet of example 4.
As shown in fig. 2, the passivation film structure of the electrotinning steel sheet of example 4 of the present invention was qualitatively analyzed by sputtering from the outside to the inside using X-ray photoelectron spectroscopy (XPS), wherein the outermost layer was chromium oxide, the intermediate layer was chromium oxide and metallic chromium, and the innermost layer was metallic chromium.
It should be noted that, in the embodiment, the existence of the metal chromium enhances the uniformity of the distribution of the passivation film layer and the performance stability, is beneficial to improving the performance stability and the anti-aging performance of the electrotinning steel plate in the storage and transportation process, and simultaneously ensures good paint film adhesion and better sulfur resistance in the application process.
Fig. 3 schematically shows an X photoelectron spectrum of the passivation film layer depth distribution of the tin-electroplated steel sheet of comparative example 2.
As shown in fig. 3, in comparative example 2, the passivation film structure of the electrotinning steel plate of comparative example 2 of the present invention was qualitatively analyzed by sputtering from the outside inwards layer by layer using X-ray photoelectron spectroscopy (XPS), and the passivation film layer of the conventional electrotinning steel plate used in comparative example 2 was mainly chromium oxide, and no significant metallic chromium signal was detected. The passivation film layer lacks a firm support structure formed by metal chromium, the stability and the aging resistance of the passivation film layer are obviously reduced, and the storage and transportation period is also short. In addition, the structure is difficult to ensure that the electrotinning steel plate has good paint film adhesion and sulfur resistance.
It should be noted that the combination of the features in the present application is not limited to the combination described in the claims of the present application or the combination described in the specific examples, and all the features described in the present application may be freely combined or combined in any manner unless contradicted by each other.
It should also be noted that the above-mentioned embodiments are only specific embodiments of the present invention. It is apparent that the present invention is not limited to the above embodiments and similar changes or modifications thereto which can be directly or easily inferred from the disclosure of the present invention by those skilled in the art are intended to be within the scope of the present invention.
Claims (13)
1. The tin-electroplated steel plate comprises a steel substrate and a tin-plated layer, and is characterized in that the tin-plated layer comprises a pure tin layer and a tin-iron alloy transition layer positioned between the pure tin layer and the steel substrate, the surface of the tin-plated layer is covered with a passive film, and the passive film contains 3.5-36 mg/m 2 The chromium content includes a metallic chromium content and a chromium oxide content.
2. The tin-electroplated steel sheet of claim 1, characterized in that the content of metallic chromium in the passive film is 1.0-16 mg/m 2 。
3. The tin-electroplated steel sheet according to claim 1, characterized in that the tin-electroplated steel sheet has a single-side tin-electroplating amount of 0.3-16 g/m 2 。
4. A passivation treatment solution for forming the passivation film on the surface of the tin-electroplated steel sheet as set forth in any one of claims 1 to 3, wherein a solvent of the passivation treatment solution is water, and the passivation treatment solution contains:
chromic anhydride with the concentration of 20-180 g/L;
an additive selected from: 0.2 to 0.8g/L sulfuric acid, 0.5 to 3.5g/L sodium sulfate, 0.8 to 2.5g/L fluosilicic acid or 1.5 to 6.5g/L sodium fluosilicate.
5. The passivating treatment solution of claim 4, wherein in the passivating treatment solution: the concentration of chromic anhydride is 20-80 g/L, and the additive is 0.2-0.8 g/L sulfuric acid; or
The concentration of chromic anhydride is 55-125 g/L, and the additive is 0.5-3.5 g/L sodium sulfate; or alternatively
The concentration of chromic anhydride is 75-150 g/L, and the additive is 0.8-2.5 g/L fluosilicic acid; or alternatively
The concentration of chromic anhydride is 75-180 g/L, and the additive is 1.5-6.5 g/L sodium fluosilicate.
6. The method for manufacturing an electrolytic tin plated steel sheet according to any one of claims 1 to 3, comprising the steps of:
(1) Carrying out electrotinning treatment on the steel substrate to form a tinned layer;
(2) Carrying out reflow treatment on the tin-plated steel plate;
(3) Sequentially carrying out surface treatment on the tin-plated steel plate according to the following steps to form the passive film on the surface of the tin-plated steel plate:
(a) Adopting a passivation treatment solution to pre-soak the tin-plated steel plate;
(b) Carrying out cathode electrolysis treatment on the tin-plated steel plate by adopting a passivation treatment solution;
(c) Adopting a passivation treatment solution to dip the tin-plated steel plate again;
wherein the solvent of the passivation solution is water, and the passivation solution contains: chromic anhydride with the concentration of 20-180 g/L; an additive selected from: sulfuric acid with the concentration of 0.2-0.8 g/L, or sodium sulfate with the concentration of 0.5-3.5 g/L, or fluosilicic acid with the concentration of 0.8-2.5 g/L, or sodium fluosilicate with the concentration of 1.5-6.5 g/L;
(4) Rinsing and oiling.
7. The manufacturing method according to claim 6, wherein in the passivation treatment solution:
the concentration of chromic anhydride is 20-80 g/L, and the additive is 0.2-0.8 g/L sulfuric acid; or alternatively
The concentration of chromic anhydride is 55-125 g/L, and the additive is 0.5-3.5 g/L sodium sulfate; or
The concentration of chromic anhydride is 75-150 g/L, and the additive is 0.8-2.5 g/L fluosilicic acid; or alternatively
The concentration of chromic anhydride is 75-180 g/L, and the additive is 1.5-6.5 g/L sodium fluosilicate.
8. The manufacturing method according to claim 6, wherein in the step (2), the tin-plated steel sheet is reflowed by resistance reflow and/or induction reflow.
9. The production method according to claim 6, wherein in the step (3), the treatment time of the pre-impregnation is 1 to 5 times as long as the treatment time of the cathodic electrolysis; the treatment time of the impregnation in the step (c) is 2 to 9 times of the cathodic electrolysis treatment time.
10. The production method according to claim 6, wherein in the step (3), the cathodic electrolysis treatment time is 0.05 to 0.3s.
11. The production method according to claim 6, wherein in the step (3), the current density of the cathodic electrolysis treatment is 20A/dm 2 ～100A/dm 2 。
12. The manufacturing method according to claim 6, wherein the passivation solution is used at a temperature of 32 ℃ to 65 ℃.
13. The manufacturing method according to claim 6, wherein in the step (4), the oil is applied by electrostatic oiling, and the amount of the oil applied is controlled to be 1.5mg/m 2 ～9.5mg/m 2 。
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| CN202111184833.4A CN115961317A (en) | 2021-10-12 | 2021-10-12 | Electrotinning steel plate and manufacturing method thereof |
| PCT/CN2022/124792 WO2023061395A1 (en) | 2021-10-12 | 2022-10-12 | Tin-electroplated steel plate and manufacturing method therefor |
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| CN202111184833.4A CN115961317A (en) | 2021-10-12 | 2021-10-12 | Electrotinning steel plate and manufacturing method thereof |
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Cited By (1)
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| CN117187900A (en) * | 2023-11-03 | 2023-12-08 | 江苏省沙钢钢铁研究院有限公司 | Coated tin plate for eight-treasure porridge pot and manufacturing method thereof |
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| LU77061A1 (en) * | 1977-04-01 | 1979-01-18 | ||
| CN108796584B (en) * | 2017-04-28 | 2020-08-25 | 宝山钢铁股份有限公司 | Flexible control method for surface passivation film structure of tinned product |
| CN110885999A (en) * | 2018-09-10 | 2020-03-17 | 上海梅山钢铁股份有限公司 | Chromic acid passivation method for cold-rolled electroplated tin steel plate |
| CN112538591B (en) * | 2019-09-23 | 2022-04-15 | 上海梅山钢铁股份有限公司 | Cold-rolled electroplated tin steel plate with excellent coating performance and manufacturing method thereof |
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| CN117187900A (en) * | 2023-11-03 | 2023-12-08 | 江苏省沙钢钢铁研究院有限公司 | Coated tin plate for eight-treasure porridge pot and manufacturing method thereof |
| CN117187900B (en) * | 2023-11-03 | 2024-02-09 | 江苏省沙钢钢铁研究院有限公司 | Coated tin plate for eight-treasure porridge pot and manufacturing method thereof |
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