WO2023061395A1 - 一种电镀锡钢板及其制造方法 - Google Patents

一种电镀锡钢板及其制造方法 Download PDF

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WO2023061395A1
WO2023061395A1 PCT/CN2022/124792 CN2022124792W WO2023061395A1 WO 2023061395 A1 WO2023061395 A1 WO 2023061395A1 CN 2022124792 W CN2022124792 W CN 2022124792W WO 2023061395 A1 WO2023061395 A1 WO 2023061395A1
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tin
concentration
passivation
steel plate
treatment solution
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PCT/CN2022/124792
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English (en)
French (fr)
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魏军胜
李秀军
兰剑
李鹏
王章薇
陈红星
苗馥峻
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宝山钢铁股份有限公司
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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • 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

Definitions

  • the invention relates to a composite material and a manufacturing method thereof, in particular to an electro-tinned steel plate and a manufacturing method thereof.
  • electroplated tinplate is a product with complex production technology, long manufacturing process, high quality requirements and difficult manufacture.
  • This kind of electroplated tinplate is generally coated with a layer of pure tin on both sides of cold-rolled low-carbon thin steel plate. be made of.
  • the tin in electroplated tinplate is non-toxic, and has the characteristics of high strength, good formability, excellent corrosion resistance, strong weldability, and good printing and coloring properties, users usually use this electroplated tinplate In the field of food or beverage packaging that requires high-temperature cooking and sterilization processing, such as making metal food cans or beverage cans.
  • the tin plating layer may include a tin-iron alloy transition layer and a pure tin layer.
  • tin is easy to oxidize in the air, in order to ensure the good performance of the tinned steel plate, it is usually necessary to further passivate the surface of the tinned steel plate to form a functional protective layer, that is, a passivation film; Passivation treatment can effectively improve the corrosion resistance and sulfide blackening resistance of electroplated tin plate, and endow the electroplated tin plate with good finishing performance.
  • the traditional passivation method of tin-plated steel plate is: electrolytic treatment of the steel plate in a dichromate solution.
  • the chromium in the dichromate solution is electrolyzed to be reduced to trivalent chromium oxide or metallic chromium, which is deposited on the surface of the tin layer of the tin-plated steel sheet.
  • the basic passivation process parameters are as follows: the passivation solution contains 25 ⁇ 5g/L sodium dichromate (H 2 Cr 2 O 7 ), the temperature of the passivation solution is 42 ⁇ 5°C, the pH value is 4 ⁇ 1, and the passivation time is about For 1s, the passivation electric quantity is 3C/dm 2 .
  • Tin-plated steel with this surface treatment can be used in many ways. However, with the development of printing and coating equipment and technology, can making equipment and technology, and the diversification of can contents, there are more and more applications that require high coating adhesion and high sulfur resistance performance.
  • the existing passivation treatment technology of electroplated tin steel plate with sodium dichromate as the main salt is difficult to meet the requirements of high coating adhesion and high sulfur resistance performance at the same time.
  • the present invention expects to develop a new passivation treatment solution, which can be used for special surface treatment of tin-plated steel sheets, so as to obtain a product with good coating adhesion and sulfur resistance.
  • a new type of electroplated tin plate is a new passivation treatment solution, which can be used for special surface treatment of tin-plated steel sheets, so as to obtain a product with good coating adhesion and sulfur resistance.
  • the electroplated tin-plated steel plate prepared by the method of the invention has good coating adhesion and sulfur resistance, has a simple manufacturing process, is environmentally friendly and has low application cost, and has good promotion prospects and application value.
  • One of the objectives of the present invention is to provide an electro-tinned steel plate, which adopts a special surface passivation treatment. After passivation treatment, a layer of passivation film can be covered on the surface of the tin-plated layer, thereby greatly improving the surface properties of the tin-plated steel plate, thereby ensuring better film adhesion and sulfur resistance of the tin-plated steel plate.
  • the electro-tinned steel plate has excellent coating film adhesion and sulfur resistance, can be effectively applied in the field of food or beverage packaging, and has good promotion prospects and application value.
  • the present invention provides an electro-tinned steel plate, which includes a tinned steel plate and a passivation film, the tinned steel plate includes a steel substrate and a tin-coated layer, and the tin-plated layer covers the surface of the steel substrate
  • the tin-plated layer includes a pure tin layer and a tin-iron alloy transition layer between the pure tin layer and the steel substrate
  • the surface of the tin-plated layer is covered with a passivation film
  • the chromium content in the passivation film is 3.5 to 36 mg/m 2
  • the chromium content includes metal chromium content and chromium oxide content.
  • the steel substrate of the present invention is not particularly limited, and steel substrates commonly used in this field can be used.
  • the steel substrate may be a thin strip of cold rolled carbon steel.
  • the content of metallic chromium in the passivation film is 1.0 to 16 mg/m 2 .
  • an electro-tin-plated steel plate with good film adhesion and sulfur resistance can be obtained.
  • the electro-tin-plated steel plate can be effectively used in the field of food or beverage packaging, and has the advantages of Good promotion prospect and application value.
  • the amount of tin plating on one side of the steel substrate is 0.3 to 16 g/m 2 .
  • another object of the present invention is to provide a kind of passivation treatment solution, this passivation treatment solution can carry out surface treatment to tinplate steel plate, to form passivation film on the surface of tinplate steel plate, the formed passivation film has good Excellent surface stability, which can optimize the coating adhesion and sulfur resistance of electroplated tin plate.
  • the present invention provides a passivation treatment solution, which is used for surface treatment of the steel plate to form a passivation film (such as the passivation film in the above-mentioned tin-plated steel plate) on the surface of the steel plate, wherein the The solvent of the passivation treatment solution is water, and the passivation treatment solution contains:
  • Additives selected from the group consisting of: sulfuric acid at a concentration of 0.2 to 0.8 g/L, sodium sulfate at a concentration of 0.5 to 3.5 g/L, fluosilicic acid at a concentration of 0.8 to 2.5 g/L, 1.5 to 6.5 g/L of sodium fluorosilicate.
  • the passivation film formed by using the passivation treatment solution of the present invention to treat the surface of the tin-plated steel plate has good surface stability, and can effectively optimize the film adhesion and sulfur resistance of the tin-plated steel plate.
  • the concentration of the chromic anhydride is 20 to 80 g/L, and the additive is sulfuric acid of 0.2 to 0.8 g/L; or
  • the concentration of the chromic anhydride is 55 to 125 g/L, and the additive is sodium sulfate of 0.5 to 3.5 g/L; or
  • the concentration of the chromic anhydride is 75 to 150 g/L, and the additive is 0.8 to 2.5 g/L of fluosilicic acid; or
  • the concentration of the chromic anhydride is 75 to 180 g/L, and the additive is sodium fluorosilicate at 1.5 to 6.5 g/L.
  • another object of the present invention is to provide a method for manufacturing the above-mentioned tin-plated steel sheet.
  • the manufacturing method is simple and environmentally friendly, and the above-mentioned electro-tinned steel sheet of the present invention can be effectively produced by using the method.
  • the present invention provides a kind of method for manufacturing electroplated tin plate, it comprises the steps:
  • Electrotinning is carried out to the steel substrate to form a tin-plated steel plate with a tin-plated layer on the steel substrate;
  • the solvent of the passivation treatment solution is water
  • the passivation treatment solution contains: chromic anhydride with a concentration of 20 to 180 g/L; and an additive selected from: sulfuric acid with a concentration of 0.2 to 0.8 g/L, Sodium sulfate at a concentration of 0.5 to 3.5 g/L, fluosilicic acid at a concentration of 0.8 to 2.5 g/L, sodium fluosilicate at a concentration of 1.5 to 6.5 g/L;
  • the steel substrate is a cold-rolled carbon steel sheet strip;
  • the cold-rolled carbon steel sheet strip has usually undergone cold rolling and annealing treatment, and some will undergo secondary cooling after completing the annealing treatment. rolled.
  • the steel substrate is subjected to tinning treatment after alkali cleaning and pickling; preferably, the main salt of the electroplating solution used in the tinning treatment is tin methanesulfonate (MSA electroplating tin system) or tin phenol sulfonate (PSA electroplating tin system), and contains necessary electroplating additives; preferably, during the tin electroplating process, the amount of tin plating on one side of the steel substrate is controlled to be 0.3 to 16g/m 2 .
  • MSA electroplating tin system tin methanesulfonate
  • PSA electroplating tin system tin phenol sulfonate
  • the reflow treatment is performed solely by resistance reflow or induction reflow, or by a combination of resistance reflow and induction reflow.
  • the tinned steel plate is sequentially pre-dipped, cathodic electrolytically treated and chemically impregnated with a passivation treatment solution to form a required cathodic electrolytic passivation film on the surface of the tinned steel plate.
  • the pre-soaking time is controlled to be 1 to 5 times the cathodic electrolytic treatment time; and/or the soaking time is controlled to be 2 to 9 times the cathodic electrolytic treatment time.
  • the use temperature of the passivation treatment solution is controlled at 32°C to 65°C.
  • the current density of the cathodic electrolytic treatment is controlled to be 20A/dm 2 to 100A/dm 2 ;
  • the material of the anode plate used in the cathodic electrolytic treatment is not particularly limited, it can be ordinary carbon steel or an inert material, Such as lead-tin alloy, platinum, iridium oxide, etc.
  • the concentration of the chromic anhydride is 20 to 80 g/L, and the additive is sulfuric acid of 0.2 to 0.8 g/L; or
  • the concentration of the chromic anhydride is 55 to 125 g/L, and the additive is sodium sulfate of 0.5 to 3.5 g/L; or
  • the concentration of the chromic anhydride is 75 to 150 g/L, and the additive is 0.8 to 2.5 g/L of fluosilicic acid; or
  • the concentration of the chromic anhydride is 75 to 180 g/L, and the additive is sodium fluorosilicate at 1.5 to 6.5 g/L.
  • step (2) reflow treatment is performed on the tinned steel sheet by means of resistance reflow and/or induction reflow.
  • the pre-soaking time in step (a) is 1 to 5 times of the cathodic electrolytic treatment time in step (b); and/or the soaking time in step (c) is the 2 to 9 times the cathodic electrolytic treatment time.
  • the cathodic electrolysis treatment time in step (b) is 0.05 to 0.3s.
  • the time for cathodic electrolytic treatment of the pre-impregnated tin-plated steel plate using a passivation treatment solution in step (b) is determined according to the amount of surface treatment layer required for the tin-plated steel plate, for example, 0.05 to 0.3s.
  • the current density of cathodic electrolytic treatment in step (b) is 20A/dm 2 to 100A/dm 2 .
  • the use temperature of the passivation treatment solution is 32°C to 65°C.
  • step (4) electrostatic oiling is used for oiling, and the amount of oiling is controlled at 1.5 mg/m 2 to 9.5 mg/m 2 .
  • step (4) the tinned steel plate that has been subjected to surface passivation treatment is rinsed, either by immersion rinsing or by spray rinsing; Blow dry.
  • the tin-plated steel sheet After rinsing and drying, the tin-plated steel sheet can be oiled. Generally, electrostatic oiling can be used, and the oiling amount can be controlled from 1.5mg/m 2 to 9.5mg/m 2 .
  • the electro-tinned steel sheet and its manufacturing method according to the present invention have the following advantages and beneficial effects:
  • the inventor creatively designed a new passivation treatment solution for surface treatment of tinned steel sheets to form a passivation film on the surface of the tinned steel sheets.
  • the passivation film thus formed has good surface stability, and even after long-term storage or hot air baking during processing, the surface tin oxide will not grow significantly.
  • the present invention can obtain a kind of new electroplated tin steel plate, the surface of the tin layer of this electrotin plated steel plate is covered with passivation film, and it has good corrosion resistance, resistance to sulfide blackening performance and acid resistance performance.
  • the electrolytic tin-plated steel sheet of the present invention has excellent coating film adhesion performance. Moreover, its manufacturing process is simple, the product is environmentally friendly and has low application cost, does not contain heavy metals and organic components that are potentially toxic to the human body, is non-toxic in contact with food, and is environmentally friendly, and can be widely used in food, beverages, chemical tanks and covers, and electronics. Therefore, it has good promotion prospect and application value.
  • Fig. 1 schematically shows the interlayer structure of the electro-tinned steel sheet according to the present invention.
  • Fig. 2 schematically shows the X-ray photoelectron spectrum of the depth distribution of the passivation film layer of the electro-tinned steel sheet according to Example 4 of the present invention.
  • Fig. 3 schematically shows the X-ray photoelectron spectrum of the depth distribution of the passivation film layer of the electrolytic tin-plated steel sheet of Comparative Example 2 of the present invention.
  • Table 1 lists the concentration ratio of each component in the passivation treatment solutions of Examples 1 to 14.
  • the concentration ratios of the components in the passivation treatment solutions of Examples 1 to 14 of the present invention all meet the preferred design control requirements of the present invention.
  • adopt the passivation treatment solution of embodiment 1 to 14 of the present invention to carry out surface treatment to tin-plated steel plate can form passivation film on the surface of tin-plated steel plate.
  • the tin-plated layer can include: a pure tin layer and a Tin-iron alloy transition layer between pure tin layer and steel substrate.
  • the interlayer structure of the tin-plated steel sheet may sequentially include: a steel substrate, a tin-iron alloy transition layer, and a pure tin layer.
  • a passivation film can be formed on the surface of the tinned steel plate, and the passivation film covers the tin-plated layer. surface, so as to obtain the electroplated tin-plated steel sheets corresponding to Examples 1 to 14 of the present invention.
  • the present invention has no special restrictions on the chemical element composition of the steel substrate of the tin-plated steel plate, and it is only necessary to control the amount of tin plating on one side of the steel substrate to be 0.3 to 16g/m 2 , and the technology of the present invention can be realized The composition system of the prior art of effect all can adopt.
  • the steel substrates of the tin-plated steel sheets in Examples 1 to 14 are the same steel material.
  • the electroplated tin-plated steel sheet of embodiment 1 to 14 all adopts following steps to make:
  • Electrotinning is carried out to the steel substrate to form a tin-plated steel sheet with a tin-plated layer on the steel substrate: the steel substrate after cold rolling and annealing and tempering treatment is carried out by alkali washing, degreasing, pickling and activating the surface, and then Electrotin plating is performed in an electroplating tin solution with tin methanesulfonate as the main salt, and the amount of tin plating on one side of the steel substrate is controlled to be 0.3 to 16g/m 2 to form a tin plating layer on the steel substrate.
  • Reflow treatment of the tin-plated steel sheet Reflow treatment of the tin-plated steel sheet is performed by resistance reflow and/or induction reflow.
  • the use temperature of the control passivation treatment solution is 32°C to 65°C;
  • the cathodic electrolysis treatment time in the control step (b) is 0.05 to 0.3s, and the current density is 20A/dm 2 to 100A/dm 2 ;
  • the control step (a) is 1 to 5 times of the cathodic electrolytic treatment time in step (b), and the soaking time in the control step (c) is 2 to 9 times of the cathodic electrolytic treatment time in step (b).
  • Rinsing and oiling Rinse and dry after passivation treatment, and then apply oil by means of electrostatic oiling, controlling the amount of oiling to be 1.5mg/m 2 to 9.5mg/m 2 .
  • Table 2 lists the relevant process parameters of the electrolytic tin-plated steel sheets of Examples 1 to 14 in the above steps.
  • Comparative Examples 1 to 2 are provided for performance comparison. It should be noted that the tin-plated steel sheets of Examples and Comparative Examples are prepared in substantially the same steps, the only difference being that Examples 1 to 14 are treated with the passivation treatment solution of the present invention, while Comparative Examples 1 to 2 Use conventional passivation treatment solutions for treatment.
  • the passivation solution contains 25 ⁇ 5g/L sodium dichromate (H 2 Cr 2 O 7 ), the temperature of the passivation solution is 42 ⁇ 5°C, The pH value is 4 ⁇ 1, the passivation time is about 1s, and the passivation electric quantity is 3C/dm 2 .
  • the electroplated tin steel sheets of Examples 1 to 14 and Comparative Examples 1 to 2 were respectively sampled.
  • the passivation film of the electroplated tin steel plate of embodiment 1 to 14 and comparative example 1 to 2 is detected, utilizes the metal chromium content, chromium oxide content and total chromium of the passivation film of the steel plate of detection embodiment and comparative example content.
  • Table 3 lists the total chromium content, metallic chromium content and chromium oxide content in the passive films of the electroplated tin steel sheets of Examples 1 to 14 and Comparative Examples 1 to 2.
  • the electrotinned steel sheets of Examples 1 to 14 and Comparative Examples 1 to 2 are further sampled to Perform the following performance tests.
  • control film thickness is 7.0g/m 2 to 8.0g/m 2 .
  • Bake and cure the coating film first bake at 185°C for 12 minutes, then bake at 205°C for 12 minutes. After the samples of Examples 1 to 14 and Comparative Examples 1 to 2 were completely cooled, they were evaluated for coating film adhesion and sulfur resistance performance. The evaluation results of coating film adhesion and sulfur resistance are shown in Table 4 below.
  • Coating film adhesion evaluation method on a scratch instrument with a screw pitch of 1.5mm, use a speed of 90r/min to 100r/min to draw a thread line with a length of 60mm to 80mm and a diameter of 10mm. The depth of the scribe line is just to penetrate the coating film. Gently brush off the scratched coating debris, use 3M610 adhesive tape to paste on the thread, and press the adhesive tape to make it completely bonded to the coating film. Then fix the coating film model, the adhesive tape is torn off from the coating film rapidly in the upward direction, and observe the area where the coating film is torn off from the tin-plated steel sheets of Examples 1 to 14 and Comparative Examples 1 to 2.
  • Anti-sulfur performance evaluation method Weigh 0.50g of L-cysteine hydrochloride (C 3 H 8 NO 2 SCl), 3.60g of potassium dihydrogen phosphate (KH 2 PO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ) 7.2 g or 18 g of disodium hydrogen phosphate dodecahydrate (Na 2 HPO 4 ⁇ 12H 2 O) were respectively dissolved in water, mixed and diluted to 1000 mL to prepare a test solution. The test solution was used within 4h after preparation. All samples have the same length and a width of 30mm. Repeatedly fold the samples into squares with a spacing of 20mm to 30mm. When folding, ensure that the bend is at an angle of about 180°.
  • Table 4 lists the relevant performance evaluation results of the tin-plated steel sheets of Examples 1 to 14 and Comparative Examples 1 to 2.
  • ⁇ indicates that the corresponding performance is poor; “ ⁇ ” indicates that the corresponding performance is average; “ ⁇ ” indicates that the corresponding performance is good; “ ⁇ ” indicates that the corresponding performance is very good.
  • embodiments 1 to 14 adopt the passivation treatment solution designed by the present invention and the corresponding passivation process, and the electroplated tin-plated steel sheets of embodiments 1 to 14 obtained after surface passivation treatment It has a passivation film, which covers the surface of the tin plating layer, and its chromium content is 3.5 to 36 mg/m 2 , the chromium content includes metal chromium content and chromium oxide content, and the metal chromium content in the passivation film is 1.0 to 16 mg/m 2 .
  • the obtained tinned steel sheet has good coating adhesion and good sulfur resistance.
  • Fig. 1 schematically shows the interlayer structure of the electro-tinned steel sheet according to the present invention.
  • the interlayer structure of the tin-plated steel sheet according to the present invention may sequentially include: steel substrate 1, tin-iron alloy transition layer 2, pure tin layer 3, passivation Membrane 4 and oil layer 5.
  • the passivation film 4 covers the surface of the pure tin layer 3, and the passivation film 4 contains chromium and its oxides.
  • Fig. 2 schematically shows the X-ray photoelectron spectrum of the depth distribution of the passivation film layer on the electro-tinned steel sheet of Example 4.
  • XPS X-photoelectron spectroscopy
  • the presence of metallic chromium enhances the uniformity and stable performance of the passivation film layer, which is conducive to improving the stable performance and aging resistance of the electroplated tin-plated steel sheet during storage and transportation. At the same time, it ensures good coating adhesion and good sulfur resistance during application.
  • Fig. 3 schematically shows the X-ray photoelectron spectrum of the depth distribution of the passivation film layer of the electrolytic tin-plated steel sheet of Comparative Example 2.
  • comparative example 2 utilize X-photoelectron spectroscopy (XPS) to sputter layer by layer from the outside to the inside, qualitatively analyze the passivation film structure of the electrolytic tin-plated steel plate of comparative example 2 of the present invention, comparative example 2 adopts
  • the passivation film layer of the conventional tin-plated steel plate is mainly chromium oxide, and no obvious metal chromium signal is detected.
  • XPS X-photoelectron spectroscopy

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Abstract

本发明公开了一种电镀锡钢板，其包括镀锡钢板和钝化膜，所述镀锡钢板包括钢基板和镀锡层，所述镀锡层覆盖在所述钢基板表面上，所述镀锡层包括纯锡层和位于纯锡层和钢基板之间的锡铁合金过渡层，所述镀锡层的表面覆盖有钝化膜，所述钝化膜中的铬含量为3.5至36mg/m 2，所述铬含量包括金属铬含量和氧化铬含量。本发明还公开了一种钝化处理溶液，其用于形成上述电镀锡钢板中的钝化膜，所述钝化处理溶液的溶剂为水，所述钝化处理溶液含有：浓度为20至180g/L的铬酐；和添加剂，其选自：浓度为0.2至0.8g/L的硫酸、浓度为0.5至3.5g/L的硫酸钠、浓度为0.8至2.5g/L的氟硅酸、浓度为1.5至6.5g/L的氟硅酸钠。此外，本发明还公开了制造上述电镀锡钢板的方法。

Description

一种电镀锡钢板及其制造方法 技术领域
本发明涉及一种复合材料及其制造方法，尤其涉及一种电镀锡钢板及其制造方法。
背景技术
众所周知，电镀锡钢板是一种生产技术复杂、制造流程长、质量要求高且制造难度大的产品，这种电镀锡钢板一般通过在冷轧低碳薄钢板的双面各镀覆一层纯锡制得。
在现有技术中，由于电镀锡钢板中的锡无毒，且具有强度高、成形性好、耐蚀性能优良、焊接性强、印刷着色性良好的特性，用户通常将这种电镀锡钢板用于需要经过高温蒸煮杀菌加工的食品或饮料包装领域中，例如制作金属食品罐或饮料罐。
在生产电镀锡钢板的过程中，钢基板一般需要经过前处理、电镀锡处理和软熔处理，以获得镀锡钢板；在完成上述工艺之后，镀锡钢板可以形成镀锡层，且所形成的镀锡层可以包括锡铁合金过渡层和纯锡层。
由于锡在空气中易于氧化，为了保证电镀锡钢板具有良好的使用性能，通常需要对电镀锡钢板表面进一步进行钝化处理，以形成功能性保护层，即钝化膜；通过对电镀锡钢板进行钝化处理可以有效提升电镀锡钢板的耐蚀性能、耐硫化黑变性能，并赋予电镀锡钢板良好的涂饰性能。
目前，传统的电镀锡钢板的钝化方法是：在重铬酸盐溶液中对钢板进行电解处理。重铬酸盐溶液中的铬被电解以还原成三价铬的氧化物或金属铬，从而沉积在镀锡钢板的锡层表面。基本钝化工艺参数如下：钝化液含有25±5g/L重铬酸钠(H 2Cr 2O 7)，钝化液温度为42±5℃，pH值为4±1，钝化时间约为1s，钝化电量为3C/dm 2。
采用这种表面处理方式处理的镀锡钢可以满足很多方面的用途。但是，随着印涂装备及技术、制罐装备及技术以及罐头内容物多样化的发展，需要高涂膜附着力、高抗硫性能要求的应用场合越来越多。现有的以重铬酸钠为主盐的电镀锡钢板钝化处理技术很难同时满足高涂膜附着力和高抗硫性能的要求。
基于以上原因，本发明期待开发一种新的钝化处理溶液，该钝化处理溶液可以用于对镀锡钢板进行特殊的表面处理，从而获得一种具备良好的涂膜附着力和抗硫性能的新型电镀锡钢板。
通过本发明方法制得的电镀锡钢板具备良好的涂膜附着力和抗硫性能，其制造过程简 单，产品环保且应用成本低，具有良好的推广前景和应用价值。
发明内容
本发明的目的之一在于提供一种电镀锡钢板，该电镀锡钢板采用了特殊的表面钝化处理。经钝化处理后可以在镀锡层的表面覆盖一层钝化膜，从而大大提升了电镀锡钢板的表面性能，由此确保电镀锡钢板获得更加优良的涂膜附着力和抗硫性能。
该电镀锡钢板的涂膜附着力和抗硫性能优异，其可以有效应用于食品或饮料包装领域中，具有良好的推广前景和应用价值。
为了实现上述目的，本发明提供了一种电镀锡钢板，其包括镀锡钢板和钝化膜，所述镀锡钢板包括钢基板和镀锡层，所述镀锡层覆盖在所述钢基板表面上，所述镀锡层包括纯锡层和位于纯锡层和钢基板之间的锡铁合金过渡层，所述镀锡层的表面覆盖有钝化膜，所述钝化膜中的铬含量为3.5至36mg/m 2，所述铬含量包括金属铬含量和氧化铬含量。
本发明的钢基板没有特别限制，可使用本领域常用的钢基板。例如，钢基板可以为冷轧碳钢薄板带。
优选地，钝化膜中的金属铬含量为1.0至16mg/m 2。
本发明通过在电镀锡钢板的镀锡层表面覆盖钝化膜，可获得具备良好涂膜附着力和抗硫性能的电镀锡钢板，该电镀锡钢板可以有效应用于食品或饮料包装领域中，具有良好的推广前景和应用价值。
优选地，在本发明所述的电镀锡钢板中，所述钢基板上的单面镀锡量为0.3至16g/m 2。
此外，本发明的另一目的在于提供一种钝化处理溶液，该钝化处理溶液可以对镀锡钢板进行表面处理，以在镀锡钢板表面形成钝化膜，所形成的钝化膜具有良好的表面稳定性能，能够优化电镀锡钢板的涂膜附着力和抗硫性能。
为了实现上述目的，本发明提供了一种钝化处理溶液，其用于对钢板进行表面处理，以在钢板表面形成钝化膜(例如上述电镀锡钢板中的钝化膜)，其中，所述钝化处理溶液的溶剂为水，所述钝化处理溶液含有：
浓度为20至180g/L的铬酐；以及
添加剂，其选自：浓度为0.2至0.8g/L的硫酸、浓度为0.5至3.5g/L的硫酸钠、浓度为0.8至2.5g/L的氟硅酸、浓度为1.5至6.5g/L的氟硅酸钠。
采用本发明上述钝化处理溶液对镀锡钢板进行表面处理所形成的钝化膜具有良好的表面稳定性能，其能够有效优化电镀锡钢板的涂膜附着力和抗硫性能。
优选地，在所述钝化处理溶液中：
所述铬酐的浓度为20至80g/L，所述添加剂为0.2至0.8g/L的硫酸；或者
所述铬酐的浓度为55至125g/L，所述添加剂为0.5至3.5g/L的硫酸钠；或者
所述铬酐的浓度为75至150g/L，所述添加剂为0.8至2.5g/L的氟硅酸；或者
所述铬酐的浓度为75至180g/L，所述添加剂为1.5至6.5g/L的氟硅酸钠。
相应地，本发明的又一目的在于提供一种制造上述电镀锡钢板的方法。该制造方法简单且环保，采用该方法可以有效制得本发明上述的电镀锡钢板。
为了实现上述目的，本发明提供了一种制造电镀锡钢板的方法，其包括如下步骤：
(1)对钢基板进行电镀锡处理，形成钢基板上具有镀锡层的镀锡钢板；
(2)对镀锡钢板进行软熔处理；
(3)依次按照如下步骤对经软熔处理的镀锡钢板进行表面处理，在镀锡钢板表面形成钝化膜：
(a)采用钝化处理溶液对镀锡钢板进行预浸渍；
(b)采用钝化处理溶液对经预浸渍的镀锡钢板进行阴极电解处理；以及
(c)采用钝化处理溶液对经阴极电解处理的镀锡钢板进行浸渍；
其中，所述钝化处理溶液的溶剂为水，所述钝化处理溶液含有：浓度为20至180g/L的铬酐；以及添加剂，其选自：浓度为0.2至0.8g/L的硫酸、浓度为0.5至3.5g/L的硫酸钠、浓度为0.8至2.5g/L的氟硅酸、浓度为1.5至6.5g/L的氟硅酸钠；
(4)漂洗和涂油。
优选地，在步骤(1)中，钢基板为冷轧碳钢薄板带；冷轧碳钢薄板带通常已经经过冷轧轧制及退火处理，有的在完成退火处理后还会经过二次冷轧。
优选地，在步骤(1)中，钢基板在经过碱洗和酸洗后，进行电镀锡处理；优选地，电镀锡处理中所采用的电镀溶液的主盐为甲基磺酸锡(MSA电镀锡体系)或者苯酚磺酸锡(PSA电镀锡体系)，并含有必要的电镀添加剂；优选地，电镀锡处理过程中，控制钢基板上的单面镀锡量为0.3至16g/m 2。
优选地，在步骤(2)中，软熔处理单独采用电阻软熔或感应软熔进行，或者采用电阻软熔与感应软熔的组合进行。
优选地，在步骤(3)中，依次采用钝化处理溶液对镀锡钢板进行预浸渍、阴极电解处理和化学浸渍，在镀锡钢板表面形成所需的阴极电解钝化膜。优选地，控制预浸渍时间为阴极电解处理时间的1至5倍；和/或控制浸渍时间为阴极电解处理时间的2至9倍。
优选地，在步骤(3)中，钝化处理溶液的使用温度控制为32℃至65℃。
优选地，在步骤(3)中，控制阴极电解处理的电流密度为20A/dm 2至100A/dm 2；阴 极电解处理所采用的阳极板材质没有特别限定，可以是普碳钢或惰性材料，例如铅锡合金、铂金、氧化铱等。
优选地，在所述钝化处理溶液中：
所述铬酐的浓度为20至80g/L，所述添加剂为0.2至0.8g/L的硫酸；或者
所述铬酐的浓度为55至125g/L，所述添加剂为0.5至3.5g/L的硫酸钠；或者
所述铬酐的浓度为75至150g/L，所述添加剂为0.8至2.5g/L的氟硅酸；或者
所述铬酐的浓度为75至180g/L，所述添加剂为1.5至6.5g/L的氟硅酸钠。
优选地，在步骤(2)中，采用电阻软熔和/或感应软熔的方式对镀锡钢板进行软熔处理。
优选地，在步骤(3)中，步骤(a)中预浸渍时间为步骤(b)中阴极电解处理时间的1至5倍；和/或步骤(c)中浸渍时间为步骤(b)中阴极电解处理时间的2至9倍。
优选地，在步骤(3)中，步骤(b)中阴极电解处理时间为0.05至0.3s。
优选地，在步骤(3)中，步骤(b)中采用钝化处理溶液对经预浸渍的镀锡钢板进行阴极电解处理的时间依据镀锡钢板所需的表面处理层的量决定，例如可以为0.05至0.3s。
优选地，在步骤(3)中，步骤(b)中阴极电解处理的电流密度为20A/dm 2至100A/dm 2。
优选地，所述钝化处理溶液的使用温度为32℃至65℃。
优选地，在步骤(4)中，采用静电涂油的方式涂油，涂油量控制为1.5mg/m 2至9.5mg/m 2。
优选地，在步骤(4)中，对经过表面钝化处理的镀锡钢板进行漂洗处理，可以采用浸渍漂洗，也可以采用喷淋漂洗；优选地，在漂洗处理后可以通过热风干燥、蒸汽喷吹等进行吹干。
完成漂洗及干燥后，可以对镀锡钢板进行涂油处理，一般可以采用静电涂油方式，涂油量可以控制为1.5mg/m 2至9.5mg/m 2。
相较于现有技术，本发明所述的电镀锡钢板及其制造方法具有如下所述的优点以及有益效果：
发明人创造性地设计了一种新的钝化处理溶液，用于对镀锡钢板进行表面处理，以在镀锡钢板表面形成一种钝化膜。由此形成的钝化膜具有良好的表面稳定性能，即使经过长时间存储或在加工过程中经过热风烘烤，表面锡氧化物也不会有明显的增长。
利用上述钝化处理溶液，本发明可以获得一种新的电镀锡钢板，该电镀锡钢板的镀锡层表面覆盖有钝化膜，其具有良好的耐蚀性能，抗硫化黑变性能和抗酸性能。
相应地，本发明所述的电镀锡钢板的涂膜附着力性能优良。而且，其制造过程简单，产品环保且应用成本低，不含对人体有潜在毒性的重金属和有机物成分，食品接触无毒，对环境友好，可广泛应用于食品、饮料、化工罐和盖以及电子器件等领域中，因此具有良 好的推广前景和应用价值。
附图说明
图1示意性地显示了本发明所述的电镀锡钢板的层间结构示意图。
图2示意性地显示了本发明实施例4的电镀锡钢板的钝化膜层深度分布的X光电子能谱图。
图3示意性地显示了本发明比较例2的电镀锡钢板的钝化膜层深度分布的X光电子能谱图。
具体实施方式
下面将结合具体的实施例和说明书附图对本发明所述的电镀锡钢板及其制造方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
实施例1至14
表1列出了实施例1至14的钝化处理溶液中各组分的浓度配比。
表1
Figure PCTCN2022124792-appb-000001
如表1所示，本发明实施例1至14的钝化处理溶液中的各组分的浓度配比均符合本发明优选的设计控制要求。在本发明中，采用本发明所述实施例1至14的钝化处理溶液对镀 锡钢板进行表面处理，可在镀锡钢板的表面形成钝化膜。需要说明的是，在本发明中，可以选自现有技术中已有的钢基板进行电镀锡处理，以形成镀锡层，制得镀锡钢板；镀锡层可以包括：纯锡层和位于纯锡层和钢基板之间的锡铁合金过渡层。由此，镀锡钢板的层间结构可以依次包含有：钢基板、锡铁合金过渡层、纯锡层。
在本发明中，采用本发明所述实施例1至14的钝化处理溶液对镀锡钢板进行表面处理后，可以在镀锡钢板的表面形成钝化膜，钝化膜覆盖在镀锡层的表面，从而获得本发明实施例1至14所对应的电镀锡钢板。
需要说明的是，本发明对镀锡钢板的钢基板的化学元素成分没有特别限制，仅需控制钢基板上的单面镀锡量为0.3至16g/m 2即可，能够实现本发明的技术效果的现有技术的成分体系都可以采用。其中，在本发明中，实施例1至14中镀锡钢板的钢基板为同一种钢材。
在本发明中，实施例1至14的电镀锡钢板均采用以下步骤制得：
(1)对钢基板进行电镀锡处理，形成钢基板上具有镀锡层的镀锡钢板：将经过冷轧轧制和退火调质处理后的钢基板进行碱洗脱脂、酸洗活化表面，然后在以甲基磺酸锡为主盐的电镀锡溶液中进行电镀锡处理，并控制钢基板上的单面镀锡量为0.3至16g/m 2，以在钢基板上形成镀锡层。
(2)对镀锡钢板进行软熔处理：采用电阻软熔和/或感应软熔对镀锡钢板进行软熔处理。
(3)依次按照如下步骤对经软熔处理的镀锡钢板进行表面处理，在镀锡钢板表面形成钝化膜：
(a)采用钝化处理溶液对镀锡钢板进行预浸渍；
(b)采用钝化处理溶液对经预浸渍的镀锡钢板进行阴极电解处理；以及
(c)采用钝化处理溶液对经阴极电解处理的镀锡钢板进行浸渍；
其中，控制钝化处理溶液的使用温度为32℃至65℃；控制步骤(b)中阴极电解处理时间为0.05至0.3s、电流密度为20A/dm 2至100A/dm 2；控制步骤(a)中预浸渍时间为步骤(b)中阴极电解处理时间的1至5倍，控制步骤(c)中浸渍时间为步骤(b)中阴极电解处理时间的2至9倍。
(4)漂洗和涂油：钝化处理后进行漂洗和干燥，然后采用静电涂油的方式涂油，控制涂油量为1.5mg/m 2至9.5mg/m 2。
表2列出了实施例1至14的电镀锡钢板在上述步骤中的相关工艺参数。
表2
Figure PCTCN2022124792-appb-000002
相应地，为了验证本发明实施例1至14的电镀锡钢板的优异性能，提供了比较例1至2进行性能比较。需要说明的是，实施例和比较例的电镀锡钢板采用基本相同的步骤进行制备，区别仅在于：实施例1至14采用本发明所述的钝化处理溶液进行处理，而比较例1至2采用常规钝化处理溶液进行处理。比较例1至2中的常规钝化处理溶液及相关工艺参数如下：钝化液含有25±5g/L重铬酸钠(H 2Cr 2O 7)，钝化液温度为42±5℃，pH值为4±1，钝化时间约为1s，钝化电量为3C/dm 2。
对实施例1至14和比较例1至2的电镀锡钢板分别取样。对实施例1至14和比较例1至2的电镀锡钢板的钝化膜进行检测，利用X荧光法检测实施例和比较例的钢板的钝化膜的金属铬含量、氧化铬含量和总铬含量。
表3列出了实施例1至14和比较例1至2的电镀锡钢板的钝化膜中的总铬含量、金属铬含量和氧化铬含量。
表3
Figure PCTCN2022124792-appb-000003
相应地，在完成对实施例1至14和比较例1至2的电镀锡钢板的钝化膜的检测之后，进一步对实施例1至14和比较例1至2的电镀锡钢板进行取样，以进行如下性能测试。
在本发明中，采用刮涂方式将常规环氧酚醛涂料涂覆于实施例1至14和比较例1至2的样品钢板的表面，并控制膜厚为7.0g/m 2至8.0g/m 2。对涂膜进行烘烤固化：先在185℃下烘烤12分钟，再在205℃下烘烤12分钟。待实施例1至14和比较例1至2的样品完全冷却后，对其进行涂膜附着力和抗硫性能的评估。涂膜附着力和抗硫性能的评价结果列于下表4中。
涂膜附着力评估方法：在螺距为1.5mm的划痕仪上，用90r/min至100r/min的速度，划出长度为60mm至80mm、直径为10mm的螺纹线。划线深度以刚好穿透涂膜为度。轻轻刷去划掉的涂膜碎屑，使用3M610粘胶带粘贴在螺纹线上，压紧粘胶带使之与涂膜完全粘合。然后固定住涂膜样板，将粘胶带以斜上方向迅速从涂膜上撕下，观察涂膜从实施例1至14和比较例1至2的电镀锡钢板上被撕下的面积。
抗硫性能评估方法：称取L型半胱氨酸盐酸盐(C 3H 8NO 2SCl)0.50g、磷酸二氢钾(KH 2PO 4)3.60g、磷酸氢二钠(Na 2HPO 4)7.2g或十二水磷酸氢二钠(Na 2HPO 4·12H 2O)18g，分别用水溶解后，混合并稀释至1000mL，由此制备试验溶液。试验溶液在配制后4h 内使用。所有样片的长度相同且宽度为30mm，将样片反复折叠成间距为20mm至30mm的方块，折叠时确保弯曲处约呈180°夹角。折叠时确保待测面被折叠至外弯曲面处，以便于进行后续观察。将制备好的样片浸没于盛满试验溶液的耐压容器中，将该容器加盖密封。应确保实验用试剂液面距容器的盖内面距离为5mm至7mm。将该容器置于压力蒸汽灭菌器内，在121℃条件下蒸煮60分钟。自然冷却后用工业纯水冲洗干净，冷风吹干表面，观察实施例1至14和比较例1至2的电镀锡钢板的表面硫化黑变(即硫化斑)情况。
表4列出了实施例1至14和比较例1至2的电镀锡钢板的相关性能评价结果。
表4
编号 涂膜附着力 抗硫性能
实施例1 ◎ ○
实施例2 ◎ ○
实施例3 ◎ ○
实施例4 ◎ ○
实施例5 ◎ ○
实施例6 ◎ ○
实施例7 ◎ ○
实施例8 ◎ ○
实施例9 ◎ ○
实施例10 ◎ ○
实施例11 ◎ ○
实施例12 ◎ ○
实施例13 ◎ ○
实施例14 ◎ ○
比较例1 △ ○
比较例2 ○ ╳
注：“╳”表示对应性能较差；“△”表示对应性能一般；“○”表示对应性能较好；“◎”表示对应性能很好。
由本发明表3和表4可以看出，实施例1至14采用本发明设计的钝化处理溶液及相应的钝化工艺，经表面钝化处理后获得的实施例1至14的电镀锡钢板覆合有钝化膜，该钝化膜覆盖在镀锡层的表面，其铬含量为3.5至36mg/m 2，该铬含量包括金属铬含量和氧化铬含量，钝化膜中金属铬的含量为1.0至16mg/m 2。所获得镀锡钢板具备很好的涂膜附着力和较好的抗硫性能。
不同于实施例1至14，比较例1至2的电镀锡钢板的钝化膜量较高时，具备较好的抗硫性能，但是涂膜附着力一般；钝化膜量较低时，涂膜附着力较好，但是抗硫性能较差。
图1示意性地显示了本发明所述的电镀锡钢板的层间结构示意图。
如图1所示，在本发明所述的电镀锡钢板中，本发明所述的电镀锡钢板的层间结构可以依次包括：钢基板1、锡铁合金过渡层2、纯锡层3、钝化膜4和油层5。其中，钝化膜4覆盖在纯锡层3的表面，且钝化膜4中含有铬及其氧化物。
图2示意性地显示了实施例4的电镀锡钢板的钝化膜层深度分布的X光电子能谱图。
如图2所示，利用X光电子能谱(XPS)从外向内逐层溅射，定性分析本发明实施例4的电镀锡钢板的钝化膜结构，其最外层为氧化铬，中间层为氧化铬和金属铬，最内层为金属铬。
需要说明的是，在本实施方式中，金属铬的存在，增强了钝化膜层的分布的均匀性和性能稳定，有利于提升电镀锡钢板在储运过程中的性能稳定和抗时效性能，同时保证应用过程中很好的涂膜附着力和较好的抗硫性能。
图3示意性地显示了比较例2的电镀锡钢板的钝化膜层深度分布的X光电子能谱图。
如图3所示，在比较例2中，利用X光电子能谱(XPS)从外向内逐层溅射，定性分析本发明比较例2的电镀锡钢板的钝化膜结构，比较例2所采用的常规电镀锡钢板的钝化膜层主要为氧化铬，没有检测到明显的金属铬信号。钝化膜层中缺少金属铬形成的坚固支撑结构，其稳定性和抗时效性就会明显降低，因此储运周期也比较短。另外，这种结构也很难确保电镀锡钢板同时具备较好的涂膜附着力和抗硫性能。
需要说明的是，本发明中各技术特征的组合方式并不限本发明权利要求中所记载的组合方式或是具体实施方式所记载的组合方式，本发明记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。
还需要注意的是，以上所列举的实施例仅为本发明的具体实施例。显然本发明不局限于以上实施例，随之做出的类似变化或变形是本领域技术人员能从本发明公开的内容直接得出或者很容易便联想到的，均应属于本发明的保护范围。

Claims (13)

  1. 一种电镀锡钢板，其包括镀锡钢板和钝化膜，所述镀锡钢板包括钢基板和镀锡层，其特征在于，所述镀锡层覆盖在所述钢基板表面上，所述镀锡层包括纯锡层和位于纯锡层和钢基板之间的锡铁合金过渡层，所述镀锡层的表面覆盖有钝化膜，所述钝化膜中的铬含量为3.5至36mg/m 2，所述铬含量包括金属铬含量和氧化铬含量。
  2. 根据权利要求1所述的电镀锡钢板，其特征在于，所述钝化膜中的金属铬含量为1.0至16mg/m 2。
  3. 根据权利要求1所述的电镀锡钢板，其特征在于，所述钢基板上的单面镀锡量为0.3至16g/m 2。
  4. 一种钝化处理溶液，其特征在于，所述钝化处理溶液用于形成权利要求1至3中任一项所述的电镀锡钢板中的所述钝化膜，所述钝化处理溶液的溶剂为水，所述钝化处理溶液含有：
    浓度为20至180g/L的铬酐；以及
    添加剂，所述添加剂选自：浓度为0.2至0.8g/L的硫酸、浓度为0.5至3.5g/L的硫酸钠、浓度为0.8至2.5g/L的氟硅酸、浓度为1.5至6.5g/L的氟硅酸钠。
  5. 根据权利要求4所述的钝化处理溶液，其特征在于，在所述钝化处理溶液中：
    所述铬酐的浓度为20至80g/L，所述添加剂为0.2至0.8g/L的硫酸；或者
    所述铬酐的浓度为55至125g/L，所述添加剂为0.5至3.5g/L的硫酸钠；或者
    所述铬酐的浓度为75至150g/L，所述添加剂为0.8至2.5g/L的氟硅酸；或者
    所述铬酐的浓度为75至180g/L，所述添加剂为1.5至6.5g/L的氟硅酸钠。
  6. 一种制造权利要求1至3中任一项所述的电镀锡钢板的方法，其特征在于，所述方法包括如下步骤：
    (1)对钢基板进行电镀锡处理，形成钢基板上具有镀锡层的镀锡钢板；
    (2)对镀锡钢板进行软熔处理；
    (3)依次按照如下步骤对经软熔处理的镀锡钢板进行表面处理，在镀锡钢板表面形成钝化膜：
    (a)采用钝化处理溶液对镀锡钢板进行预浸渍；
    (b)采用钝化处理溶液对经预浸渍的镀锡钢板进行阴极电解处理；以及
    (c)采用钝化处理溶液对经阴极电解处理的镀锡钢板进行浸渍；
    其中，所述钝化处理溶液的溶剂为水，所述钝化处理溶液含有：浓度为20至180g/L的铬酐；以及添加剂，所述添加剂选自：浓度为0.2至0.8g/L的硫酸、 浓度为0.5至3.5g/L的硫酸钠、浓度为0.8至2.5g/L的氟硅酸、浓度为1.5至6.5g/L的氟硅酸钠；
    (4)漂洗和涂油。
  7. 根据权利要求6所述的方法，其特征在于，在所述钝化处理溶液中：
    所述铬酐的浓度为20至80g/L，所述添加剂为0.2至0.8g/L的硫酸；或者
    所述铬酐的浓度为55至125g/L，所述添加剂为0.5至3.5g/L的硫酸钠；或者
    所述铬酐的浓度为75至150g/L，所述添加剂为0.8至2.5g/L的氟硅酸；或者
    所述铬酐的浓度为75至180g/L，所述添加剂为1.5至6.5g/L的氟硅酸钠。
  8. 根据权利要求6所述的方法，其特征在于，在步骤(2)中，采用电阻软熔和/或感应软熔的方式对镀锡钢板进行软熔处理。
  9. 根据权利要求6所述的方法，其特征在于，在步骤(3)中，步骤(a)中预浸渍时间为步骤(b)中阴极电解处理时间的1至5倍；步骤(c)中浸渍时间为步骤(b)中阴极电解处理时间的2至9倍。
  10. 根据权利要求6所述的方法，其特征在于，在步骤(3)中，步骤(b)中阴极电解处理时间为0.05至0.3s。
  11. 根据权利要求6所述的方法，其特征在于，在步骤(3)中，步骤(b)中阴极电解处理的电流密度为20A/dm 2至100A/dm 2。
  12. 根据权利要求6所述的方法，其特征在于，在步骤(3)中，所述钝化处理溶液的使用温度为32℃至65℃。
  13. 根据权利要求6所述的方法，其特征在于，在步骤(4)中，采用静电涂油的方式涂油，涂油量为1.5mg/m 2至9.5mg/m 2。
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