CN113529141B - Tin-chromium composite coating steel plate and preparation method thereof - Google Patents
Tin-chromium composite coating steel plate and preparation method thereof Download PDFInfo
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- CN113529141B CN113529141B CN202110672730.6A CN202110672730A CN113529141B CN 113529141 B CN113529141 B CN 113529141B CN 202110672730 A CN202110672730 A CN 202110672730A CN 113529141 B CN113529141 B CN 113529141B
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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
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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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
Abstract
The invention discloses a tin-chromium composite coating steel plate and a preparation method thereof, wherein the method comprises the following steps: flattening the annealed steel plate to obtain a steel substrate with the roughness of 0.2-0.4 mu m; pre-electroplating and tin electroplating a steel substrate to obtain a tin-plated steel plate; the pre-electroplating solution comprises methanesulfonic acid and stannous methanesulfonate, and the electroplating tin adopts methanesulfonic acid electroplating solution; passivating and oiling the tin-plated steel plate to obtain a tin-chromium composite plated steel plate; the passivation comprises a first passivation and a second passivation, and the first passivation solution comprises: 100-150g/L CrO 3 0.4-0.6g/L of H 2 SO 4 4-6g/L of Na 2 FSi 6 And the second passivation solution comprises: 50-80g/L CrO 3 0.05-0.15g/L of H 2 SO 4 0.04-0.06g/L of Na 2 FSi 6 . The tin-chromium composite plating steel plate has good corrosion resistance, good welding performance and good finishing performance.
Description
Technical Field
The invention relates to the technical field of steel preparation, in particular to a tin-chromium composite coating steel plate and a preparation method thereof.
Background
The tin plate and the chromium plate are main materials which are currently applied to packaging steel, the tin plate is obtained by putting a steel plate in molten tin liquid for hot dipping or electroplating, the surface of the tin plate is bright, but the application range of the tin plate is limited due to the defect of poor corrosion resistance; compared with tin plate, the chromium plate has the advantages of low production cost, good corrosion resistance and good coating adhesion, but the chromium plate has poor welding performance, so that the application of the chromium plate is greatly limited. The composite coating product for food packaging with good quality needs to meet the requirements of good corrosion resistance, welding performance and coating performance, and the existing composite coating product for food packaging is difficult to simultaneously meet the requirements of good corrosion resistance, welding performance and coating performance.
Therefore, how to produce a tin-chromium composite plated steel plate with good corrosion resistance, welding performance and coating performance becomes a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a tin-chromium composite plating steel plate and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing a tin-chromium composite plated steel sheet, the method comprising:
flattening the annealed steel plate to obtain a steel substrate with the roughness of 0.2-0.4 mu m;
pre-electroplating and electroplating tin on the steel substrate with the roughness of 0.2-0.4 mu m to obtain a tin-coated steel plate; the pre-electroplating solution adopted by the pre-electroplating comprises methanesulfonic acid and stannous methanesulfonate, and the electroplating tin adopts a methanesulfonic acid electroplating solution;
passivating and oiling the tin-plated steel plate to obtain a tin-chromium composite plated steel plate; wherein the passivating comprises: carrying out first passivation by adopting a first passivation solution, and then carrying out second passivation by adopting a second passivation solution, wherein the first passivation solution comprises the following final concentration components: 100-150g/L CrO 3 0.4-0.6g/L of H 2 SO 4 4-6g/L of Na 2 FSi 6 The second passivation solution comprises the following components in final concentration: 50-80g/L CrO 3 0.05-0.15g/L of H 2 SO 4 0.04-0.06g/L of Na 2 FSi 6 。
Further, the leveling adopts a double-frame wet leveling mode, the double-frame comprises a first frame adopting a texturing roller with the roughness of 1.1-1.3 μm and a second frame adopting a grinding roller with the roughness of 0.3-0.5 μm, and the distribution ratio of the stretch ratio of the straightening and the leveling is (0.8-1.2): (0.8-1.2).
Further, the pre-plating solution comprises the following components in final concentration: 4-6g/L of methanesulfonic acid, 5-15mg/L of Sn 2+ 。
Further, the immersion cleaning temperature of the pre-electroplating is 35-45 ℃.
Further, the methane sulfonic acid plating solution comprises the following components in final concentration: 20-30g/L Sn 2+ 30-50ml/L of methanesulfonic acid, 10-20ml/L of antioxidant and 2-5ml/L of additive, wherein the additive comprises at least one of polyoxyethylene, polyethylene glycol and sodium dodecyl benzene sulfonate.
Further, the current density of the electrolytic tin plating is 5-10A/dm 2 The temperature of the electrolytic tinning is 35-45 ℃.
Further, the temperature of the first passivation is 40-45 ℃, and the current density of the first passivation is 55-65A/dm 2 。
Further, the temperature of the second passivation is 40-45 ℃, and the current density of the second passivation is 15-25A/dm 2 。
The invention also provides a tin-chromium composite coating steel plate, which comprises the following components:
a steel substrate having a roughness of 0.2-0.4 μm;
the tin-chromium composite coating is coated on the surface of the steel substrate and comprises a metal chromium layer, a metal tin layer and a hydrated chromium oxide layer, wherein each m of the tin-chromium composite coating is 2 The mass of the metal tin in the steel substrate is 0.1-0.8g, the mass of the metal chromium is 30-50mg, and the mass of the hydrated chromium oxide is 5-12mg; the metallic tin layer is in an island shape with the diameter of 0.2-1.5 mu m.
Further, the chemical composition of the steel substrate comprises the following components in percentage by mass: c:0.02 to 0.06%, si:0.01-0.02%, mn:0.1-0.5%, P:0.012-0.015%, S:0.008-0.015%, als:0.025 to 0.085 percent of Cu, less than or equal to 0.2 percent of Ni, less than or equal to 0.15 percent of Cr, less than or equal to 0.1 percent of Mo, less than or equal to 0.0035 percent of N, less than or equal to 0.003 percent of O, and the balance of Fe and inevitable impurities.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a tin-chromium composite coating steel plate and a preparation method thereof, wherein the method comprises the following steps: flattening the annealed steel plate to obtain a steel substrate with the roughness of 0.2-0.4 mu m; pre-electroplating and tin electroplating are carried out on the steel substrate with the roughness of 0.2-0.4 mu m to obtain a tin-plated steel plate; the pre-electroplating solution adopted by the pre-electroplating comprises methanesulfonic acid and stannous methanesulfonate, and the electroplating tin adopts a methanesulfonic acid electroplating solution; passivating and oiling the tin-plated steel plate to obtain a tin-chromium composite plated steel plate; wherein the passivating comprises: carrying out first passivation by adopting a first passivation solution, and then carrying out second passivation by adopting a second passivation solution, wherein the first passivation solution comprises the following final concentration components: 100-150g/L CrO 3 0.4-0.6g/L of H 2 SO 4 4-6g/L of Na 2 FSi 6 The second passivation solution comprises the following components in final concentration: 50-80g/L CrO 3 0.05-0.15g/L of H 2 SO 4 0.04-0.06g/L of Na 2 FSi 6 . The embodiment of the invention controls the roughness of the steel substrate to be 0.2-0.4 μm, which is beneficial to the distribution uniformity of the composite plating and improves the corrosion resistance of the product; by innovatively using methanesulfonic acidAnd stannous methanesulfonate are used as pre-electroplating liquid, play a role in activating the strip steel and are beneficial to island-shaped deposition of a tin layer; the tin electroplating process adopts environment-friendly MSA methane sulfonic acid electroplating solution to obtain island-shaped tin with the diameter of 0.2-1.5 mu m, and greatly improves the welding performance of the composite plating plate; the two-step passivation method is favorable for accurately controlling the contents of the simple substance chromium layer and the chromium oxide layer, so that the coating performance is improved, and the tin-chromium composite coating steel plate has good corrosion resistance, good welding performance and good coating performance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method for manufacturing a tin-chromium composite coated steel plate according to an embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating a tin-chromium composite coated steel sheet according to an embodiment of the present invention; 1-steel substrate; 21-a metallic chromium layer; 22-metallic tin layer; 23-hydrated chromium oxide layer; 24-oil film;
fig. 3 is an electron microscope image of island-shaped tin contained tin of a tin-chromium composite plated steel sheet provided by an embodiment of the invention.
Detailed Description
The present invention will be specifically explained below in conjunction with specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly presented thereby. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
according to an exemplary embodiment provided by an embodiment of the present invention, there is provided a method for manufacturing a tin-chromium composite plated steel sheet, as shown in fig. 1, the method including:
s1, flattening the annealed steel plate to obtain a steel substrate with the roughness of 0.2-0.4 mu m;
the roughness of the steel substrate is 0.2-0.4 μm, which is beneficial to the distribution uniformity of the composite coating and improves the corrosion resistance of the product; if the roughness of the steel substrate is less than 0.2 mu m, the adhesive force performance of the composite coating product in downstream coating and printing use is adversely affected; if the roughness of the steel substrate is more than 0.4 mu m, the uniform distribution of island-shaped tin is not facilitated, and the welding performance and the corrosion resistance are influenced; the purpose of the roll matching mode and the elongation rate distribution of the wet flattening process is to control the roughness of a steel substrate to be 0.2-0.4 mu m;
as an alternative embodiment, the leveling is a double-stand wet leveling method, the double stand comprises a stand using a roughening roller with a roughness of 1.1-1.3 μm and a stand using a grinding roller with a roughness of 0.3-0.5 μm, and the distribution ratio of the elongation ratio of the straightening and the leveling is (0.8-1.2): (0.8-1.2). The roller distribution mode of double-frame wet leveling and the elongation rate distribution are favorable for the uniformity of the distribution of the composite coating, and the corrosion resistance of the product is improved;
if the roughness of the roughened roller is less than 1.1 mu m, the roughness of the steel substrate is less than 0.2 mu m; if it is more than 1.3 μm, it results in a steel substrate roughness of more than 0.4. Mu.m; the roughness of the texturing roller is preferably 1.2 μm;
if the roughness of the grinding roller is less than 0.3 mu m, the roughness of the steel substrate is more than 0.4 mu m; if it is more than 0.5. Mu.m, it results in a steel substrate roughness of less than 0.2. Mu.m; the roughness of the grinding roller is preferably 0.4 μm;
if the elongation ratio distribution ratio is less than 0.8:1.2, resulting in a steel substrate roughness below 0.2 μm; if the ratio is more than 1.2:0.8, resulting in a steel substrate roughness greater than 0.4 μm; the elongation ratio distribution ratio is preferably 1:1;
s2, pre-electroplating and electrotinning the steel substrate with the roughness of 0.2-0.4 mu m to obtain a tin-plated steel plate; the pre-electroplating solution adopted by the pre-electroplating comprises methanesulfonic acid and stannous methanesulfonate, and the electroplating tin adopts a methanesulfonic acid electroplating solution;
according to the embodiment of the invention, methanesulfonic acid and stannous methanesulfonate are innovatively adopted as the pre-electroplating solution, so that the action of activating the strip steel is achieved, nucleation sites during tin electroplating are provided, and island-shaped deposition of a tin layer is facilitated; in particular, the amount of the solvent to be used,
the pre-plating solution comprises the following components in final concentration: 4-6g/L of methanesulfonic acid, 5-15mg/L of Sn 2+ . The methanesulfonic acid is used for removing an oxide layer on the surface of the strip steel, if the concentration of the methanesulfonic acid is too low, the oxide layer is not completely removed, the deposition of a tin layer is influenced, and if the concentration of the methanesulfonic acid is too high, the adverse influence of damaging the surface of the substrate is caused; sn (tin) 2+ The function of the tin-plating solution is to enrich the surface of the activated strip steel and increase nucleation sites when tin is electroplated, if Sn is 2+ If the concentration is too low, island-like deposition of tin layer is not favored in the tin electroplating stage, if Sn is 2+ Too high a concentration may inhibit the influence of methanesulfonic acid on the activation of the strip.
The pre-plating process is only immersion cleaning and is not electrified, and the pre-plating temperature is 35-45 ℃. The pre-electroplating condition is favorable for increasing nucleation sites during tin electroplating and is favorable for island formation and distribution uniformity of tin layer deposition.
The tin electroplating process of the embodiment of the invention adopts environment-friendly MSA methane sulfonic acid electroplating solution to obtain island-shaped tin with the diameter of 0.2-1.5 mu m, thereby greatly improving the welding performance of the composite plating plate; in particular, the amount of the solvent to be used,
the methane sulfonic acid electroplating solution comprises the following components in final concentration: 20-30g/L Sn 2+ 30-50ml/L of methanesulfonic acid, 10-20ml/L of antioxidant and 2-5ml/L of additive, wherein the additive comprises at least one of polyoxyethylene, polyethylene glycol and sodium dodecyl benzene sulfonate. Sn (tin) 2+ For providing cathodic electrodepositionMain salt of (b), if Sn 2+ Too low concentration, fine crystal, not good for island-like tin formation, if Sn 2+ The over-high concentration causes the reduction of the dispersion capability of the plating solution, aggravates the edge effect and is not beneficial to the uniform distribution of the plating layer; the additive has the functions of increasing cathode polarization and refining crystal grains, hydrogen evolution is easy to occur if the concentration of the additive is too low, and island-shaped tin cannot be formed if the concentration of the additive is too high;
the current density of the electrolytic tin plating is 5-10A/dm 2 The temperature of the electrolytic tinning is 35-45 ℃.
The embodiment of the invention applies 2-5ml/L of low-concentration additive and 5-10A/dm 2 The current density is low, so that the size of tin crystal grains is coarsened, island-shaped tin with the size of 0.2-1.5 mu m can be obtained, and the welding performance of the composite plating plate is greatly improved;
s3, passivating and oiling the tin-plated steel plate to obtain a tin-chromium composite plated steel plate; wherein the passivating comprises: carrying out first passivation by adopting a first passivation solution, and then carrying out second passivation by adopting a second passivation solution, wherein the first passivation solution comprises the following final concentration components: 100-150g/L CrO 3 0.4-0.6g/L of H 2 SO 4 4-6g/L of Na 2 FSi 6 The second passivation solution comprises the following components in final concentration: 50-80g/L CrO 3 0.05-0.15g/L of H 2 SO 4 0.04-0.06g/L of Na 2 FSi 6 。
The adoption of a two-step passivation method is favorable for accurately controlling the contents of the simple substance chromium layer and the chromium oxide layer to obtain the optimal metal chromium layer and the optimal chromium oxide layer, and particularly, every m can be ensured 2 The mass of the metal tin in the steel substrate is 0.1-0.8g, the mass of the metal chromium is 30-50mg, and the mass of the hydrated chromium oxide is 5-12mg ", so that the finishing performance is improved.
In the embodiment of the invention, crO is in the second passivation solution 3 ，H 2 SO 4 ，Na 2 FSi 6 The concentrations of the three components are all lower than the concentrations of the three components in the first passivation solution for the reasons that: the high-concentration passivation solution is matched with high current density to form simple substance chromium, and the low-concentration passivation solution is matched with low current density to form chromium oxide layer;
according to another exemplary embodiment of the embodiments of the present invention, there is provided a tin-chromium composite plated steel sheet, as shown in fig. 2, including:
a steel substrate 1, wherein the roughness of the steel substrate is 0.2-0.4 μm;
the tin-chromium composite coating 2 is coated on the surface of the steel substrate and comprises a metal chromium layer 21, a metal tin layer 22 and a hydrated chromium oxide layer 23, wherein each m of the tin-chromium composite coating is 2 The mass of the metal tin in the steel substrate is 0.1-0.8g, the mass of the metal chromium is 30-50mg, and the mass of the hydrated chromium oxide is 5-12mg; the metallic tin layer is in an island shape with the diameter of 0.2-1.5 mu m.
The surface of the hydrated chromium oxide layer 23 is also covered with an oil film 24.
The embodiment of the invention controls the roughness of the steel substrate to be 0.2-0.4 μm, which is beneficial to the distribution uniformity of the composite plating and improves the corrosion resistance of the product; island-shaped tin with the diameter of 0.2-1.5 mu m greatly improves the welding performance of the composite plating plate; "per m 2 The mass of the metal tin in the steel substrate is 0.1-0.8g, the mass of the metal chromium is 30-50mg, the mass of the hydrated chromium oxide is 5-12mg, and the contents of a simple substance chromium layer and a chromium oxide layer are precisely controlled to obtain the optimal metal chromium layer and the optimal chromium oxide layer, so that the coating performance is improved.
The tin-chromium composite plated steel plate provided by the embodiment of the invention can be prepared by the preparation method of the tin-chromium composite plated steel plate provided by the embodiment of the invention, but other methods which can be developed in the future can be adopted, as long as the method can ensure that the roughness of a steel substrate is 0.2-0.4 mu m, and a metal tin layer in the tin-chromium composite plated layer is in an island shape with the diameter of 0.2-1.5 mu m, and each m is an island shape 2 The mass of the metal tin in the steel substrate is 0.1-0.8g, the mass of the metal chromium is 30-50mg, and the mass of the hydrated chromium oxide is 5-12mg; therefore, the tin-chromium composite plating steel plate has good corrosion resistance, good welding performance and good finishing performance.
The tin-chromium composite coating steel plate provided by the embodiment of the invention is mainly used for food packaging and can also be used for chemical barrels or spray cans.
As an alternative embodiment, the steel substrate has the following chemical composition in mass fraction: ranges of common chemical compositions for steel substrates for food packaging, for example: c:0.02 to 0.06%, si:0.01-0.02%, mn:0.1-0.5%, P:0.012-0.015%, S:0.008-0.015%, als:0.025 to 0.085 percent of Cu, less than or equal to 0.2 percent of Ni, less than or equal to 0.15 percent of Cr, less than or equal to 0.1 percent of Mo, less than or equal to 0.0035 percent of N, less than or equal to 0.003 percent of O, and the balance of Fe and inevitable impurities.
A tin-chromium composite plated steel sheet and a method for manufacturing the same according to the present application will be described in detail with reference to examples, comparative examples, and experimental data.
Example 1
S1, adopting a one-time cold-rolled continuous annealing plate T-4CA with the thickness specification of 0.20mm and the width specification of 832mm, and flattening the annealed steel plate after the strip steel is annealed to obtain a steel substrate with the roughness of 0.35 mu m; the leveling adopts a double-frame wet leveling process, one frame adopts a roughening roller, the roughness is 1.2 mu m, the two frames adopt grinding rollers, the roughness is 0.4 mu m, and the elongation percentage distribution is 1:1;
s2, pre-electroplating and electrotinning the steel substrate with the roughness of 0.35 mu m to obtain a tin-plated steel plate; wherein the pre-plating solution in the pre-plating process contains 4g/L of methanesulfonic acid, sn 2+ The concentration is 5mg/L; the tinning section adopts MSA electroplating solution, and the electroplating process condition is Sn 2+ The concentration is 20g/L, the methanesulfonic acid is 30ml/L, the additive is 2ml/L, the antioxidant is 10ml/L, the solution temperature is controlled at 35 ℃, and the current density is 5A/dm 2 ；
S3, passivating and oiling the tin-plated steel plate to obtain a tin-chromium composite plated steel plate; wherein, the passivation adopts a two-step method, and the first passivation process conditions are as follows: passivating solution CrO 3 Concentration of 100g/L, passivation temperature of 40 ℃ and H 2 SO 4 Concentration 0.5g/L, na 2 FSi 6 The concentration is 5g/L, and the current density is 60A/dm 2 And the second passivation process condition is as follows: passivating solution CrO 3 Concentration of 50g/L, passivation temperature of 40 ℃, H 2 SO 4 Concentration of0.1g/L，Na 2 FSi 6 The concentration is 0.05g/L, and the current density is 20A/dm 2 。
The finally obtained Sn-Cr composite coating steel plate has the roughness of 0.35 mu m and the tin plating amount of 0.15g/m 2 Island size 0.3 μm, amount of metallic chromium 35mg/m 2 The amount of hydrated chromium oxide is 8mg/m 2 The salt spray grade is 1 grade, the adhesive force is 1 grade, the sulfur resistance is 1 grade, and the welding performance is good when the paint is applied to a protein beverage can.
Example 2
S1, adopting a one-time cold rolling continuous annealing plate T-5CA with the thickness specification of 0.20mm and the width specification of 870mm, and flattening the annealed steel plate after the strip steel is annealed to obtain a steel substrate with the roughness of 0.4 mu m; the leveling adopts a wet leveling process, one machine frame adopts a roughening roller, the roughness is 1.1 mu m, the other machine frame adopts a grinding roller, the roughness is 0.3 mu m, and the elongation percentage distribution is 0.8 during leveling: 1.2;
s2, pre-electroplating and electrotinning the steel substrate with the roughness of 0.4 mu m to obtain a tin-plated steel plate; wherein the pre-plating solution in the pre-plating process contains 5g/L of methylsulfonic acid, sn 2+ The concentration is 10mg/L; the tinning section adopts MSA electroplating solution, and the electroplating process condition is Sn 2+ The concentration is 25g/L, the methanesulfonic acid is 40ml/L, the additive is 4ml/L, the antioxidant is 15ml/L, the solution temperature is controlled at 40 ℃, and the current density is 8A/dm 2 ；
S3, passivating and oiling the tin-plated steel plate to obtain a tin-chromium composite plated steel plate; wherein, the passivation adopts a two-step method, and the first passivation process conditions are as follows: passivating solution CrO 3 Concentration of 120g/L, passivation temperature of 42 ℃, H 2 SO 4 Concentration 0.5g/L, na 2 FSi 6 The concentration is 5g/L, and the current density is 60A/dm 2 And the second passivation process condition is as follows: passivating solution CrO 3 Concentration 65g/L, passivation temperature 42 ℃, H 2 SO 4 Concentration 0.1g/L, na 2 FSi 6 The concentration is 0.05g/L, and the current density is 20A/dm 2 。
The finally obtained Sn-Cr composite coating steel plate has the roughness of 0.4 mu m and the tin plating amount of 0.6g/m 2 The tin layer is island-shaped, the size is 0.5 mu m, and the amount of the metal chromium is 35mg/m 2 The amount of hydrated chromium oxide is 10mg/m 2 Salt spray grade 1, adhesive force grade 1 and sulfur resistance grade 1, and is applied to eight-treasure porridge pots and has good welding performance.
Example 3
S1, adopting a one-time cold rolling cover to remove a T-3BA plate, wherein the thickness specification is 0.23mm, the width specification is 906mm, and flattening the annealed steel plate after the annealing of the strip steel is finished to obtain a steel substrate with the roughness of 0.2 mu m; the leveling adopts a wet leveling process, one machine frame adopts a roughening roller, the roughness is 1.3 mu m, the other machine frame adopts a grinding roller, the roughness is 0.5 mu m, and the elongation percentage distribution is 1.2 during leveling: 0.8;
s2, pre-electroplating and electrotinning the steel substrate with the roughness of 0.2 mu m to obtain a tin-plated steel plate; wherein the pre-plating solution in the pre-plating process contains 6g/L of methylsulfonic acid, sn 2+ The concentration is 15mg/L; the tinning section adopts MSA electroplating solution, and the electroplating process condition is Sn 2+ The concentration is 30g/L, the methanesulfonic acid is 50ml/L, the additive is 5ml/L, the antioxidant is 20ml/L, the solution temperature is controlled at 45 ℃, and the current density is 10A/dm 2 ；
S3, passivating and oiling the tin-plated steel plate to obtain a tin-chromium composite plated steel plate; wherein, the passivation adopts a two-step method, and the first passivation process conditions are as follows: passivating solution CrO 3 Concentration of 150g/L, passivation temperature of 45 ℃ and H 2 SO 4 Concentration 0.5g/L, na 2 FSi 6 The concentration is 5g/L, and the current density is 60A/dm 2 And the second passivation process condition is as follows: passivating solution CrO 3 Concentration 80g/L, passivation temperature 45 ℃, H 2 SO 4 Concentration 0.1g/L, na 2 FSi 6 The concentration is 0.05g/L, and the current density is 20A/dm 2 。
The Sn-Cr composite coating steel plate finally obtained has the roughness of 0.2 mu m, the tin coating amount of 0.6, the island-shaped tin layer with the size of 0.6 mu m and the metal chromium amount of 50mg/m 2 The amount of hydrated chromium oxide is 12mg/m 2 . The salt spray grade is 1 grade, the adhesive force is 1 grade, and the welding performance is good when the paint is applied to a milk powder tank.
Comparative example 1
In this comparative example, the roughness of the steel substrate in step S1 was 0.1. Mu.m, and step S2 and step S3 were the same as in example 1.
Comparative example 2
In this comparative example, the roughness of the steel substrate in step S1 was 0.5. Mu.m, and step S2 and step S3 were the same as in example 1.
Comparative example 3
In this comparative example, the pre-plating solution in step S2 was 2g/L H 2 SO 4 The electroplating solution adopted by the electrotinning is a common electroplating solution: 15g/L of Sn 2+ 30-50ml/L of methanesulfonic acid, 10-20ml/L of antioxidant, 10-15ml/L of additive, step S1 and step S3 are the same as in example 1.
Comparative example 4
In the comparative example, the step S3 adopts one-step passivation, and the formula of the passivation solution is specifically 15-25g/L Na 2 Cr 2 O 7 Step S1 and step S2 are the same as in example 1.
Experimental example 1
The properties of the tin-chromium composite plated steel sheets obtained in examples 1 to 3 and comparative examples 1 to 4 were measured and counted as shown in table 1.
TABLE 1
Note: the more the welding performance index "+" indicates the better the welding performance
As can be seen from the data in Table 1:
in comparative example 1, the roughness of the steel substrate was 0.1 μm, which is less than the range of 0.2 to 0.4 μm of the inventive example, and there was a disadvantage that the adhesion of the paint film was poor;
in comparative example 2, the steel substrate having a roughness of 0.5 μm, which is greater than the range of 0.2 to 0.4 μm of the inventive example, had a disadvantage of poor corrosion resistance;
in the comparative example 3, the pre-plating solution and the electrotinning solution are common plating solutions, and have the defect of poor welding performance;
in the comparative example 4, the one-step passivation method has the defects of poor corrosion resistance, poor paint film adhesion and poor sulfur resistance;
the tin-chromium composite plating steel plate prepared in the embodiment 1-3 has good corrosion resistance, good welding performance and good finishing performance.
Fig. 3 is an electron microscope image of island-shaped tin contained in a tin-chromium composite plated steel plate provided by the embodiment of the invention, which shows that island-shaped tin with a diameter of 0.2-1.5 μm is successfully obtained by the preparation method of the tin-chromium composite plated steel plate provided by the embodiment of the invention, and the welding performance of the composite plated plate is greatly improved;
finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A preparation method of a tin-chromium composite coating steel plate is characterized by comprising the following steps:
flattening the annealed steel plate to obtain a steel substrate with the roughness of 0.2-0.4 mu m;
pre-dipping and electroplating tin on the steel substrate with the roughness of 0.2-0.4 mu m to obtain a tin-plated steel plate; wherein the pre-immersion liquid adopted by the pre-immersion comprises methanesulfonic acid and stannous methanesulfonate, and the electrolytic tinning adopts methanesulfonic acid electroplating liquid;
passivating and oiling the tin-plated steel plate to obtainObtaining a tin-chromium composite coating steel plate; wherein the passivating comprises: carrying out first passivation by adopting a first passivation solution, and then carrying out second passivation by adopting a second passivation solution, wherein the first passivation solution comprises the following final concentration components: 100-150g/L CrO 3 0.4-0.6g/L of H 2 SO 4 4-6g/L of Na 2 SiF 6 The second passivation solution comprises the following components in final concentration: 50-80g/L CrO 3 0.05-0.15g/L of H 2 SO 4 0.04-0.06g/L of Na 2 SiF 6 ；
The pre-immersion liquid comprises the following components in final concentration: 4-6g/L of methanesulfonic acid and 5-15mg/L of Sn 2+ ；
The presoaking temperature of the presoaking is 35-45 ℃;
the methane sulfonic acid electroplating solution comprises the following components in final concentration: 20-30g/L Sn 2+ 30-50ml/L of methanesulfonic acid, 10-20ml/L of antioxidant and 2-5ml/L of additive, wherein the additive comprises at least one of polyoxyethylene, polyethylene glycol and sodium dodecyl benzene sulfonate;
the current density of the electrolytic tin plating is 5-10A/dm 2 The temperature of the electrolytic tinning is 35-45 ℃.
2. The method according to claim 1, wherein the leveling is performed by a double-stand wet leveling method, the double stand comprises a first stand using a roughing roll having a roughness of 1.1 to 1.3 μm and a second stand using a grinding roll having a roughness of 0.3 to 0.5 μm, and the distribution ratio of the elongation percentage of the straightening to the elongation percentage of the leveling is (0.8 to 1.2): (0.8-1.2).
3. The method for preparing a tin-chromium composite coated steel plate as claimed in claim 1, wherein the temperature of the first passivation is 40-45 ℃, and the current density of the first passivation is 55-65A/dm 2 。
4. The method for preparing the tin-chromium composite coated steel plate as claimed in claim 1, wherein the temperature of the second passivation is 40-45 ℃, and the temperature of the second passivation is 40-45 DEG CThe current density of the secondary passivation is 15-25A/dm 2 。
5. A tin-chromium composite plated steel sheet, characterized by comprising:
a steel substrate having a roughness of 0.2-0.4 μm;
the tin-chromium composite coating is coated on the surface of the steel substrate and comprises a metal tin layer, a metal chromium layer and a hydrated chromium oxide layer, wherein each m of the tin-chromium composite coating is 2 The mass of the metal tin in the steel substrate is 0.1-0.8g, the mass of the metal chromium is 30-50mg, and the mass of the hydrated chromium oxide is 5-12mg; the metallic tin layer is in an island shape with the diameter of 0.2-1.5 mu m;
the steel substrate comprises the following chemical components in percentage by mass: c:0.02 to 0.06%, si:0.01-0.02%, mn:0.1-0.5%, P:0.012-0.015%, S:0.008-0.015%, als:0.025 to 0.085 percent of Cu, less than or equal to 0.2 percent of Ni, less than or equal to 0.15 percent of Cr, less than or equal to 0.1 percent of Mo, less than or equal to 0.0035 percent of N, less than or equal to 0.003 percent of O, and the balance of Fe and inevitable impurities.
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| JPS61130500A (en) * | 1984-11-29 | 1986-06-18 | Kawasaki Steel Corp | Production of sn/cr two-layered plated steel plate |
| CN1141420C (en) * | 2001-02-27 | 2004-03-10 | 中山中粤马口铁工业有限公司 | Process for electroplating Cr onto surface of thin steel sheet |
| CN101928966B (en) * | 2009-06-25 | 2012-12-12 | 宝山钢铁股份有限公司 | Method for plating chrome on surface of thin plate |
| CN105018976A (en) * | 2014-04-21 | 2015-11-04 | 上海梅山钢铁股份有限公司 | Cold-rolled tin plate for tank used for containing protein food and manufacturing method of cold-rolled tin plate |
| CN105648331A (en) * | 2014-11-14 | 2016-06-08 | 上海梅山钢铁股份有限公司 | Cold-rolled flash-coating tinned steel plate for food can and manufacturing method thereof |
| CN105695968A (en) * | 2015-09-30 | 2016-06-22 | 安徽中盛罐业有限公司 | Tinplate tin-plating process |
| 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 |
| CN109023445B (en) * | 2018-08-06 | 2021-04-16 | 首钢集团有限公司 | Preparation method and application of tin-plated steel plate with extremely low tin content |
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