阅读说明：本技术 一种提高镀层附着力的电镀锡液、制备方法及镀锡板 (Tin electroplating solution for improving coating adhesion, preparation method and tin plate ) 是由 黄先球 程鹏 陈红星 魏军胜 于 2021-06-29 设计创作，主要内容包括：本申请涉及电镀技术领域,尤其涉及一种提高镀层附着力的电镀锡液、制备方法及镀锡板,所述电镀锡液的组份包含稳定剂,所述稳定剂的各组份包括苯骈咪唑、硫脲、丙烷磺酸盐、乙烯氧基噻吩和乙二胺四乙酸盐；所述制备方法包括：将所述硫酸亚锡、所述苯酚磺酸和所述添加剂按比例混合,后进行预热,得到预热镀液；将所述稳定剂和所述预热镀液按比例混合,得到电镀锡液；所述镀锡板是将基板在所述电镀锡液或所述制备方法得到的电镀锡液作为电镀液中进行电镀得到的；通过在电镀锡液中加入稳定剂,使镀锡过程稳定,进而实现镀液的稳定,从而提高镀层的附着力。(The application relates to the technical field of electroplating, in particular to an electroplating tin liquid for improving the adhesion of a plating layer, a preparation method and a tin plate, wherein the components of the electroplating tin liquid comprise a stabilizer, and the stabilizer comprises benzimidazole, thiourea, propane sulfonate, ethyleneoxy thiophene and ethylenediamine tetraacetate; the preparation method comprises the following steps: mixing the stannous sulfate, the phenolsulfonic acid and the additive in proportion, and then preheating to obtain a preheated plating solution; mixing the stabilizer and the preheated plating solution in proportion to obtain an electroplating tin solution; the tin plate is obtained by electroplating a substrate in the electroplating tin solution or the electroplating tin solution obtained by the preparation method as an electroplating solution; the stabilizing agent is added into the electrolytic tinning liquid, so that the tinning process is stable, the stability of the plating liquid is further realized, and the adhesive force of the plating layer is improved.)

1. The tin electroplating solution for improving the coating adhesion is characterized by comprising a stabilizer, wherein the stabilizer comprises benzimidazole, thiourea, propane sulfonate, ethyleneoxy thiophene and ethylenediamine tetraacetate.

2. The electrolytic tin plating solution according to claim 1, wherein the propane sulfonate comprises polydithio propane sulfonate and/or mercapto propane sulfonate.

3. The electrolytic tin plating solution according to claim 1 or 2, wherein the stabilizer comprises the following components in parts by mass: 30-40% of benzimidazole, 5-10% of thiourea, 15-25% of polydithio-dipropyl sulfonate, 15-25% of mercapto-propane sulfonate, 5-10% of ethyleneoxy thiophene and 5-10% of ethylenediamine tetraacetate.

4. The tin electroplating solution according to claim 1, wherein the tin electroplating solution further comprises a stannous salt, phenolsulfonic acid and an additive.

5. The electrolytic tin plating solution according to claim 1, wherein the electrolytic tin plating solution comprises the following components in percentage by mass: 0.5 to 1 percent of stabilizer, 2.0 to 3.5 percent of stannous salt, 1.0 to 2.5 percent of phenol sulfonic acid and 0.5 to 1.0 percent of additive.

6. The tin electroplating solution according to claim 5, wherein the additive comprises alpha-naphthol polyoxyethylene ether and alpha-naphthol sulfonic acid polyoxyethylene ether.

7. The electrolytic tinning liquid according to claim 6, characterized in that the components of the additive comprise, by mass, 0.2-0.6% of alpha-naphthol polyoxyethylene ether and 0.2-0.6% of alpha-naphthol sulfonic acid polyoxyethylene ether.

8. A method for producing the electrolytic tin plating liquid according to any one of claims 1 to 7, characterized by comprising:

mixing the stannous sulfate, the phenolsulfonic acid and the additive in proportion, and then preheating to obtain a preheated plating solution;

and mixing the stabilizer and the preheating plating solution in proportion to obtain the tin electroplating solution.

9. The method for preparing a tin electroplating solution according to claim 8, wherein the temperature of the preheated plating solution is 25 ℃ to 35 ℃.

10. A tin-plated sheet having improved adhesion of a plated layer, characterized in that the tin-plated sheet is obtained by plating a substrate in the tin-plating solution according to any one of claims 1 to 7 or the tin-plating solution obtained by the production method according to any one of claims 8 to 9 as a plating solution.

Technical Field

The application relates to the technical field of electroplating, in particular to an electroplating tin liquid for improving the adhesive force of a plating layer, a preparation method and a tin plate.

Background

Tinplate is mainly used in the packaging industry, usually with a tin-iron alloy layer (FeSn)₂) Pure tin plating layer, tin oxide layer and surface oiling layer, and has beautiful appearance, high strength and light weightGood formability, and good resistance to attack by organic substances, dilute acids, alkalis and salts.

The prior tin plating technology mainly adopts a PSA-Floiseshan tin electroplating process, an anode system of the PSA-Floisan tin electroplating process is divided into a soluble anode system and an insoluble anode system, the soluble anode system has the problem of excessive plating solution, and from the production cost, the general PSA process adopts the insoluble anode system, but the insoluble anode system has the defects of unstable plating solution, influences the stability of the electrodeposition process, causes the unstable adhesion of a plating layer, and lacks the stable treatment of the plating solution at the present stage to improve the adhesion of the plating layer.

Disclosure of Invention

The application provides an electroplating tin liquid for improving the adhesive force of a plating layer, a preparation method and a tin plate, which aim to solve the technical problem that the adhesive force of the plating layer cannot be improved due to instability of the plating liquid in the prior art.

In a first aspect, the present application provides an electrotinning solution for improving the adhesion of a plating layer, wherein the components of the electrotinning solution comprise a stabilizer, and each component of the stabilizer comprises benzimidazole, thiourea, propane sulfonate, ethyleneoxy thiophene and ethylene diamine tetraacetate.

Optionally, the propane sulfonate comprises polydithio-dipropane sulfonate and/or mercapto-propane sulfonate.

Optionally, the stabilizer comprises the following components in percentage by mass: 30-40% of benzimidazole, 5-10% of thiourea, 15-25% of polydithio-dipropyl sulfonate, 15-25% of mercapto-propane sulfonate, 5-10% of ethyleneoxy thiophene and 5-10% of ethylenediamine tetraacetate.

Optionally, the tin electroplating solution further comprises a stannous salt, phenolsulfonic acid and an additive.

Optionally, the content of each component of the electrolytic tin plating solution comprises, by mass: 0.5 to 1 percent of stabilizer, 2.0 to 3.5 percent of stannous salt, 1.0 to 2.5 percent of phenol sulfonic acid and 0.5 to 1.0 percent of additive.

Optionally, the additive comprises alpha-naphthol polyoxyethylene ether and alpha-naphthol sulfonic acid polyoxyethylene ether.

Optionally, the additive comprises, by mass, 0.2% -0.6% of alpha-naphthol polyoxyethylene ether and 0.2% -0.6% of alpha-naphthol sulfonic acid polyoxyethylene ether.

In a second aspect, the present application provides a method of preparing an electrolytic tin plating solution, the method comprising:

mixing the stannous sulfate, the phenolsulfonic acid and the additive in proportion, and then preheating to obtain a preheated plating solution;

and mixing the stabilizer and the preheating plating solution in proportion to obtain the tin electroplating solution.

Optionally, the temperature of the preheated plating solution is 25-35 ℃.

In a third aspect, the present application provides a tin-plated sheet obtained by electroplating a substrate in the tin-plating solution of the first aspect or the tin-plating solution obtained by the production method of the second aspect as an electroplating solution.

Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:

according to the tin electroplating solution for improving the adhesion of the plating layer, the preparation method and the tin plate, the stabilizing agent is added into the plating solution, the benzimidazole and the thiourea added into the stabilizing agent are adsorbed on the surface of the electrode, so that the activation polarization of the tin electrodeposition process is increased, the nucleation is facilitated, and the propane sulfonate added is adsorbed with Sn in the solution and is in favor of the activation polarization of the Sn²⁺Form complex ions to change Sn²⁺By adding ethyleneoxythiophene, Sn is increased in solution as ethyleneoxythiophene is able to form a film on the substrate by the addition of ethyleneoxythiophene²⁺Adsorption of (2) promoting Sn²⁺The reduction of (2) enables the nucleation number of tin to be multiplied, and through adding the edetate, in the solution, because the edetate inhibits the impurity ferrous iron ions in the plating solution, the influence of high-medium iron impurities in the electrodeposition process is eliminated, the tin electrodeposition is facilitated to be carried out according to an instantaneous three-dimensional nucleation mode, and thus the tin plating is enabled to be carried outThe process is stable, so that the stability of the plating solution is realized, the tin coating of the tin plate is more uniform, and the adhesive force of the surface plating layer of the tin plate is improved.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.

FIG. 1 is a schematic flow chart illustrating a method for electroplating tin plating solution according to an embodiment of the present disclosure;

fig. 2 is a schematic view of a micro-morphology characteristic of a tin-iron alloy layer in a tin plate obtained by an electroplating method of a tin electroplating solution provided in example 1 of the present application;

FIG. 3 is a schematic diagram showing the experimental results of the plating adhesion of a tin-plated plate obtained by the electroplating method of the tin-plating solution provided in example 1 of the present application;

FIG. 4 is a schematic view of the micro-morphology of the tin-iron alloy layer in the tin-plated plate obtained by the electroplating method of the tin-plating solution provided in example 2 of the present application;

FIG. 5 is a schematic diagram illustrating the experimental results of coating adhesion of a tin-plated plate obtained by the electroplating method of the tin-plating solution provided in example 2 of the present application;

FIG. 6 is a schematic view of the micro-morphology of the tin-iron alloy layer in the tin-plated plate obtained by the electroplating method of the tin-plating solution provided in example 3 of the present application;

FIG. 7 is a schematic diagram showing the experimental results of the plating adhesion of a tin-plated plate obtained by the method of electroplating a tin-plating solution according to example 3 of the present application;

FIG. 8 is a schematic view of the micro-morphology of the tin-iron alloy layer in the tin-plated plate obtained by the electroplating method of the tin-plating solution provided in example 4 of the present application;

fig. 9 is a schematic diagram of a plating adhesion experimental result of a tin-plated plate obtained by an electroplating method of the tin-plating solution provided in embodiment 4 of the present application.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

In one embodiment of the application, the tin electroplating solution for improving the coating adhesion is provided, and the components of the tin electroplating solution comprise a stabilizer, wherein the stabilizer comprises benzimidazole, thiourea, propane sulfonate, ethyleneoxy thiophene and ethylene diamine tetraacetic acid salt.

In the application, the characteristics and the structure of a deposition layer obtained in the electrodeposition process basically determine the appearance, the characteristics and the structure of the coating layer and also determine the function of the coating layer, so that the adhesion of the coating layer is greatly influenced; meanwhile, the electrodeposition nucleation is divided into two cases of instantaneous nucleation and continuous nucleation, wherein the instantaneous nucleation means that the number of crystal nuclei does not change along with time, namely new nuclei are not generated in the growth process of the crystal nuclei; continuous nucleation means that the number of nuclei changes with time as a function of time, i.e., new nuclei are generated during the growth of the nuclei.

The benzimidazole and thiourea in the stabilizer are adsorbed on the surface of the motor, so that the activation polarization in the tin plating electrodeposition process is increased, nucleation is facilitated, the tin electrodeposition is carried out according to instantaneous three-dimensional nucleation growth, the nucleation number density is obviously increased, and the propane sulfonate in the stabilizer can react with Sn²⁺Complexing occurs to influence the electro-crystallization process of the tin, and the ethylene oxy thiophene in the stabilizer forms a film on the surface of the tin plate to increase Sn²⁺Adsorption of (2) promoting Sn²⁺So that the number of tin nucleation is multipliedAnd the ethylene diamine tetraacetate in the stabilizer can inhibit the ferrous ions of impurities in the plating solution, eliminate the influence of iron impurities in the high-speed tin plating solution in the electrodeposition process, and is beneficial to tin electrodeposition to be carried out according to an instantaneous three-dimensional nucleation mode, so that the tin plating process is stable, the stability of the plating solution is further realized, the tin plating layer of the tin plate is more uniform, and the adhesive force of the surface coating of the tin plate is improved.

As an alternative embodiment, the propane sulfonate includes polydithio-dipropyl sulfonate and/or mercapto-propane sulfonate, wherein the polydithio-dipropyl sulfonate may be sodium polydithio-dipropyl sulfonate and the mercapto-propane sulfonate may be sodium mercapto-propane sulfonate.

In the present application, the purpose of including polydithio-dipropyl sulfonate and mercapto-propane sulfonate by defining the specific composition of propane sulfonate is to make polydithio-dipropyl sulfonate, mercapto-propane sulfonate and Sn in the adsorbed state in the stabilizer solution in a strong synergistic effect due to the ability of dithio-dipropyl sulfonate and mercapto-propane sulfonate to form in the stabilizer²⁺Form complex ions to change Sn²⁺The effect of the complex on the tin electrodeposition process is realized.

As an optional embodiment, the content of each component of the stabilizer comprises: 30% -40% of benzimidazole, 5% -10% of thiourea, 15% -25% of polydithio-dipropyl sulfonate, 15% -25% of mercapto-propane sulfonate, 5% -10% of ethyleneoxy thiophene and 5% -10% of ethylenediamine tetraacetic acid salt, wherein the benzimidazole can be 2-mercapto-benzimidazole, the polydithio-dipropyl sulfonate can be sodium polydithio-propane sulfonate, the mercapto-propane sulfonate can be sodium mercapto-propane sulfonate, the ethyleneoxy thiophene can be 3, 4-diethyleneoxy thiophene, and the ethylenediamine tetraacetic acid salt can be disodium ethylenediamine tetraacetic acid.

In the application, the purpose of controlling the mass fraction of the 2-mercaptobenzimidazole to be 30-40% is to enable tin deposition to be carried out according to an instantaneous nucleation three-dimensional growth mode, when the mass fraction value range is too large, the 2-mercaptobenzimidazole can cover deposition active points on the surface of tin, the nucleation number density is reduced on the contrary, and when the mass fraction value range is too small, partial tin can not be carried out according to the instantaneous nucleation three-dimensional growth mode, and the nucleation number density is low.

The aim of controlling the mass fraction of thiourea to be 5-10% is to enable tin deposition to be carried out in an instantaneous nucleation three-dimensional growth mode, when the mass fraction value range is too large, the nucleation number density of tin is reduced, and when the mass fraction value range is too small, the tin deposition is carried out in a continuous nucleation mode.

The aim of controlling the mass fraction of the polydithio-dipropyl sulfonate to be 15-25 percent is to ensure that the polydithio-dipropyl sulfonate is mixed with Sn²⁺Form complex ion to change Sn²⁺When the mass fraction value range is too large, the poly-dithio-dipropyl sulfonate covers the deposition active points on the tin surface, so that the nucleation number density is reduced, and when the mass fraction value range is too small, the tin deposition is carried out in a continuous nucleation mode.

The mass fraction of the mercapto propane sulfonate is controlled to be 15-25 percent so as to be mixed with Sn²⁺Form complex ion to change Sn²⁺When the mass fraction value range is too large, the mercaptopropane sulfonate covers the deposition active sites on the tin surface, so that the nucleation number density is reduced, and when the mass fraction value range is too small, the tin deposition is carried out in a continuous nucleation mode.

The aim of controlling the mass fraction of the 3, 4-diethenyloxythiophene to be 5-10% is to increase the nucleation number of tin, when the mass fraction is in an excessively large range, the growth of crystal nuclei is hindered, and when the mass fraction is in an excessively small range, the formation of the crystal nuclei is reduced.

The purpose of controlling the mass fraction of the disodium ethylene diamine tetraacetate to be 5% -10% is to inhibit impurity ferrous ions in the plating solution, when the mass fraction value range is too large, an instant nucleation mode for inhibiting tin electrodeposition is caused, and when the mass fraction value range is too small, impurity ferrous ions in the plating solution cannot be completely inhibited.

As an optional embodiment, the tin electroplating solution comprises the following components in percentage by mass: 0.5-1% of stabilizer, 2.0-3.5% of stannous salt, 1.0-2.5% of phenolsulfonic acid and 0.5-1.0% of additive, wherein the stannous salt can be stannous sulfate.

In the application, the purpose of controlling the mass fraction of the stannous salt to be 2.0% -3.5% is to control the electrodeposition behavior of tin, when the mass fraction value range is too large, tin crystal grains become coarse, and when the mass fraction value range is too small, the current efficiency is reduced, and the conductivity becomes poor.

The purpose of controlling the mass fraction of the phenolsulfonic acid to be 1.0-2.5% is to provide SO₄ ^2-The electroplating solution keeps good conductivity and oxidation resistance, when the mass fraction value range is too large, the electroplating solution causes the deposition active points covering the tin surface, and when the mass fraction value range is too small, the electroplating solution causes the Sn resistance²⁺The oxidizing ability becomes poor.

The purpose of controlling the mass fraction of the additive to be 0.5-1.0% is to make the tin plating layer bright, when the mass fraction value range is too large, the electrodeposition of tin is inhibited, and when the mass fraction value range is too small, the tin plating layer is bright and dark.

As an alternative embodiment, the components of the additive comprise alpha-naphthol polyoxyethylene ether and alpha-naphthol sulfonic acid polyoxyethylene ether.

In the present application, the component ingredients of the limiting additive comprise alpha-naphthol polyoxyethylene ether and alpha-naphthol sulfonic acid polyoxyethylene ether for the purpose of acting as a brightener to brighten the tin coating.

As an optional embodiment, the additive comprises 0.2-0.6% of alpha-naphthol polyoxyethylene ether and 0.2-0.6% of alpha-naphthol sulfonic acid polyoxyethylene ether in parts by mass.

In the present application, the purpose of defining the mass fraction of the α -naphthol polyoxyethylene ether to be 0.2% to 0.6% is to make the tin plating layer bright, and when the mass fraction is too large, this results in suppressing electrodeposition of tin, and when the mass fraction is too small, this results in the tin plating layer bright and dull.

The purpose of limiting the mass fraction of the alpha-naphthol sulfonic acid polyoxyethylene ether to be 0.2-0.6% is to ensure that a tin coating is bright, when the mass fraction value range is too large, the electrodeposition of tin is inhibited, and when the mass fraction value range is too small, the tin coating is bright and dark.

As shown in fig. 1, in one embodiment of the present application, there is provided a method of preparing an electrolytic tin plating solution, the method including:

s1, mixing the stannous sulfate, the phenolsulfonic acid and the additive in proportion, and then preheating to obtain a preheated plating solution;

and S2, mixing the stabilizer and the preheating plating solution in proportion to obtain the electrolytic tin plating solution.

As an optional embodiment, the temperature of the preheated plating solution is 25-35 ℃.

In the present application, the purpose of controlling the temperature of the preheated plating solution to be 25-35 ℃ is to control the electroplating process of tin, and when the temperature is too large, Sn is caused²⁺When the temperature is too small, the plating efficiency is low.

In one embodiment of the present application, there is provided a tin-plated sheet obtained by electroplating a substrate in the tin-plating solution of the first aspect or the tin-plating solution obtained by the production method of the second aspect as a plating solution.

Example 1

The component content of the stabilizer comprises: 30 mass percent of 2-mercaptobenzimidazole, 10 mass percent of thiourea, 25 mass percent of sodium polydithio-dipropyl sulfonate, 25 mass percent of sodium mercaptopropane sulfonate, 5 mass percent of 3, 4-diethenoxythiophene and 5 mass percent of disodium ethylene diamine tetraacetate;

the tin electroplating solution comprises the following components in percentage by weight: 1% of stabilizer, 2.0% of stannous sulfate, 1.0% of phenol sulfonic acid and 0.5% of additive;

the additive comprises the following components in percentage by weight: 0.2 percent of alpha-naphthol polyoxyethylene ether and 0.3 percent of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Example 2

The component content of the stabilizer comprises: 40% of 2-mercaptobenzimidazole, 5% of thiourea, 15% of sodium polydithiodipropionate, 25% of sodium mercaptopropane sulfonate, 10% of 3, 4-diethenyloxythiophene and 5% of disodium ethylene diamine tetraacetate;

the tin electroplating solution comprises the following components in percentage by weight: 3.5 percent of stannous sulfate, 2.5 percent of phenol sulfonic acid and 0.7 percent of additive;

the additive comprises the following components in percentage by weight: 0.5 percent of stabilizer, 0.5 percent of alpha-naphthol polyoxyethylene ether and 0.2 percent of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Example 3

The component content of the stabilizer comprises: 35 percent of 2-mercaptobenzimidazole, 8 percent of thiourea, 20 percent of sodium polydithiodipropionate, 18 percent of sodium mercaptopropane sulfonate, 9 percent of 3, 4-diethenoxythiophene and 10 percent of disodium ethylene diamine tetraacetate;

the tin electroplating solution comprises the following components in percentage by weight: 3.0 percent of stannous sulfate, 2.0 percent of phenol sulfonic acid and 1.0 percent of additive;

the additive comprises the following components in percentage by weight: 0.75 percent of stabilizer, 0.6 percent of alpha-naphthol polyoxyethylene ether and 0.4 percent of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Example 4

The component content of the stabilizer comprises: the composition comprises 40 mass percent of 2-mercaptobenzimidazole, 7 mass percent of thiourea, 23 mass percent of sodium polydithio-dipropyl sulfonate, 15 mass percent of sodium mercaptopropane sulfonate, 7 mass percent of 3, 4-diethoxy thiophene and 8 mass percent of disodium ethylene diamine tetraacetate;

the tin electroplating solution comprises the following components in percentage by weight: 2.5 percent of stannous sulfate, 1.5 percent of phenol sulfonic acid and 0.8 percent of additive;

the additive comprises the following components in percentage by weight: 0.75 percent of stabilizer, 0.2 percent of alpha-naphthol polyoxyethylene ether and 0.6 percent of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Example 5

The component content of the stabilizer comprises: 37 mass percent of 2-mercaptobenzimidazole, 8 mass percent of thiourea, 18 mass percent of sodium polydithio-dipropyl sulfonate, 22 mass percent of sodium mercaptopropane sulfonate, 8 mass percent of 3, 4-diethenoxythiophene and 7 mass percent of disodium ethylene diamine tetraacetate;

the tin plating solution comprises the following components in percentage by weight: 2.8 percent of stannous sulfate, 2.2 percent of phenol sulfonic acid and 0.6 percent of additive;

the additive comprises the following components in percentage by weight: 1% of stabilizer, 0.3% of alpha-naphthol polyoxyethylene ether and 0.3% of alpha-naphthol sulfonic acid polyoxyethylene ether;

example 6

In the preparation method, the temperature of the preheated plating solution is controlled to be 40 ℃.

Example 7

In the preparation method, the temperature of the preheated plating solution is controlled to be 50 ℃.

Comparative example 1

No stabilizer is added; in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Comparative example 2

The component content of the stabilizer comprises: the mass fraction of the 2-mercapto benzimidazole is 50%, the mass fraction of the thiourea is 30%, the mass fraction of the sodium polydithio-dipropyl sulfonate is 0%, the mass fraction of the sodium mercaptopropane sulfonate is 0%, the mass fraction of the 3, 4-diethenyloxythiophene is 10%, and the mass fraction of the disodium ethylene diamine tetraacetate is 10%;

the tin plating solution comprises the following components in percentage by weight: 2.5 percent of stannous sulfate, 2.0 percent of phenol sulfonic acid and 1.0 percent of additive;

the additive comprises the following components in percentage by weight: 1% of stabilizer, 0.5% of alpha-naphthol polyoxyethylene ether and 0.5% of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Comparative example 3

The component content of the stabilizer comprises: the mass fraction of the 2-mercapto benzimidazole is 0%, the mass fraction of the thiourea is 0%, the mass fraction of the sodium polydithio-dipropyl sulfonate is 35%, the mass fraction of the sodium mercaptopropane sulfonate is 35%, the mass fraction of the 3, 4-diethenyloxythiophene is 15%, and the mass fraction of the disodium ethylene diamine tetraacetate is 15%;

the tin plating solution comprises the following components in percentage by weight: 3.0 percent of stannous sulfate, 1.5 percent of phenol sulfonic acid and 0.8 percent of additive;

the additive comprises the following components in percentage by weight: 2% of stabilizer, 0.2% of alpha-naphthol polyoxyethylene ether and 0.6% of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Comparative example 4

The additive comprises the following components in percentage by weight: 5% of stabilizer, 0.4% of alpha-naphthol polyoxyethylene ether and 0.4% of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 50 ℃.

Comparative example 5

The component content of the stabilizer comprises: the mass fraction of the 2-mercaptobenzimidazole is 30%, the mass fraction of the thiourea is 10%, the mass fraction of the sodium polydithio-dipropyl sulfonate is 25%, the mass fraction of the sodium mercaptopropane sulfonate is 25%, the mass fraction of the 3, 4-diethenyloxythiophene is 5%, and the mass fraction of the disodium ethylene diamine tetraacetate is 5%;

the tin plating solution comprises the following components in percentage by weight: 2.0 percent of stannous sulfate, 2.2 percent of phenol sulfonic acid and 0.5 percent of additive;

the additive comprises the following components in percentage by weight: 1% of stabilizer, 0.3% of alpha-naphthol polyoxyethylene ether and 0.2% of alpha-naphthol sulfonic acid polyoxyethylene ether;

in the preparation method, the temperature of the preheated plating solution is controlled to be 30 ℃.

Related experiments:

the tin-plated sheets obtained in examples 1 to 7 and comparative examples 1 to 5 were subjected to property tests, and the test results are shown in Table 1.

The related test method comprises the following steps: microscopic morphology of the plating layer: and (4) placing the coated steel plate in a scanning lens for observation, and counting the morphological characteristics.

Coating adhesion experiment: one side of the obtained tinned plate surface is subjected to double coating and double drying by adopting yellow epoxy type 3N2044-801YY coating produced by Suzhou three new material science and technology limited company as an inner coating, and the baking temperature is 200 ℃; and (3) performing single coating on the other surface of the obtained tinned plate by adopting CC2044-G8 light golden three-star paint produced by Suzhou three-new packaging paint Co., Ltd as an external paint, baking at 180 ℃ for 20min on both surfaces to obtain a treated tinned layer, and testing the adhesion of the tinned layer and the coating according to GB/T1720-shaped paint film adhesion test standard, and grading according to the rating standard.

TABLE 1

Categories	Topographic features	Rating
			Example 1	The grains of the coating are evenly refined, the coating is bright after reflow, and the tin-iron alloy layer grows in a columnar shape	Level 1
Example 2	The grains of the coating are evenly refined, the coating is bright after reflow, and the tin-iron alloy layer grows in a columnar shape	Level 1
			Example 3	The grains of the coating are evenly refined, the coating is bright after reflow, and the tin-iron alloy layer grows in a columnar shape	Level 1
Example 4	The grains of the coating are evenly refined, the coating is bright after reflow, and the tin-iron alloy layer grows in a columnar shape	Level 1
			Example 5	The grains of the coating are evenly refined, the coating is bright after reflow, and the tin-iron alloy layer grows in a columnar shape	Level 1
Example 6	Coarsening crystal grains of the plating layer, making the plating layer dark after reflow, and growing the tin-iron alloy layer according to columns and blocks	Grade 3
			Example 7	Coarse and uneven grains of the plating layer, gray and dark plating layer after reflow, blocky growth of the tin-iron alloy layer	4 stage
Comparative example 1	The grain size of the coating is uneven, the coating is gray after reflow, and the tin-iron alloy layer grows in a feather shape	Grade 3
			Comparative example 2	The grains of the coating are all finer, the coating is brighter after reflow, and the tin-iron alloy layer grows in a columnar shape	Stage 2
Comparative example 3	The grains of the coating are all finer, the coating is brighter after reflow, and the tin-iron alloy layer grows in a columnar shape	Stage 2
			Comparative example 4	The grains of the plating layer are rough and uneven, the plating layer is dark after reflow, and the tin-iron alloy layer grows in a block shape	4 stage
Comparative example 5	The grains of the coating are all finer, the coating is brighter after reflow, and the tin-iron alloy layer grows in a columnar shape	Stage 2

In the context of table 1, the following,

the appearance of the coating crystal grains on the surface of the obtained tin plate, the appearance of the coating after reflow and the growth state of the tin-iron alloy layer are indicated by the morphological characteristics, when the morphological characteristics are good, the coating crystal grains are explained to be uniformly refined, the coating is bright after reflow, and the growth state of the tin-iron alloy layer is consistent.

The rating means that after two surfaces of the obtained tin plate are coated with different coatings, the rating of the coating is determined according to the paint film adhesion test standard of GB/T1720-.

From the data in examples 1-7, it can be seen that:

by controlling the content of the substance in the stabilizer, the growth of the microscopic morphology of the tin-iron alloy layer in the coating of the tin-plated sheet can be controlled, as in examples 3 and 4, when the same electroplating method and similar formulation in the tin-plating solution are used.

In the case where the formulation and content of the tin plating solution are similar, the preheating temperature in the plating method is changed, and the microscopic morphology of the tin-iron alloy layer in the plated layer is different, as in example 6 and example 7.

From the data in comparative examples 1-5, it can be seen that:

from the data of comparative examples 1 and 5, it can be seen that the tin-iron alloy layer in the coating of the prepared tin plate has disordered micro-morphology and the worst coating adhesion reaches 4 grades without using a stabilizer or adding an excessive amount of a stabilizer.

One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:

(1) in the stabilizer provided by the embodiment of the application, all components can be mutually cooperated, so that not only can electroplating nucleation be controlled to be carried out according to three-dimensional nucleation growth, but also the tin electrodeposition process can be influenced, and the number of nuclei can be increased;

(2) in the electroplating method provided by the embodiment of the application, the micro-morphology of the tin-iron alloy layer in the plating layer can be controlled by controlling the addition amount of the stabilizer and the temperature of the preheated plating solution;

(3) the tin plate provided by the embodiment of the application has the characteristics that the crystal grains of the coating are uniformly refined, the coating is bright after reflow, the tin-iron alloy layer grows in a columnar shape, and the corrosion resistance of the coating is excellent, so that the performance of the tin plate is superior to that of a common coated steel plate;

(4) the components of the tin plating solution and the process conditions of the electroplating method provided by the embodiment of the application can be integrated into an automatic tin plate production line, and the automatic tin plate production with high plating layer adhesion and excellent corrosion resistance can be realized.

Drawings

Fig. 2 is a schematic view showing the microscopic morphology of the tin-iron alloy layer in the surface plating layer of the tin plate obtained in example 1 of the present application, and it can be seen from fig. 2 that the microscopic morphology of the tin-iron alloy layer in the surface plating layer of the tin plate on the surface of the tin plate obtained in example 1 grows in a columnar shape.

Fig. 3 is a schematic diagram of the result of the coating adhesion experiment of the tin plate surface coating obtained in example 1 of the present application, and it can be seen from fig. 3 that no tin oxide and chromium oxide are detected on the surface of the stripping tape, and the adhesion reaches level 1 according to the rating standard, which indicates that the coating adhesion on the surface of the tin plate is strong.

Fig. 4 is a schematic view showing the micro-morphology of the tin-iron alloy layer in the tin plate surface coating layer obtained in example 2 of the present application, and it can be seen from fig. 4 that the micro-morphology of the tin-iron alloy layer in the tin plate surface coating layer on the tin plate surface obtained in example 2 grows in a columnar shape.

Fig. 5 is a schematic diagram showing the results of the coating adhesion experiment of the tin plate surface coating obtained in example 2 of the present application, and it can be seen from fig. 5 that no tin oxide and chromium oxide are detected on the surface of the stripping tape, and the adhesion reaches level 1 according to the rating standard, which indicates that the coating adhesion on the surface of the tin plate is strong. .

Fig. 6 is a schematic view showing the microscopic morphology of the tin-iron alloy layer in the surface plating layer of the tin plate obtained in example 3 of the present application, and it can be seen from fig. 6 that the microscopic morphology of the tin-iron alloy layer in the surface plating layer of the tin plate on the surface of the tin plate obtained in example 3 grows in a columnar shape.

Fig. 7 is a schematic view of the results of the plating adhesion test on the surface of the tin plate obtained in example 3 of the present application, and it can be seen from fig. 7 that tin oxide and chromium oxide are not detected on the surface of the release tape, and the adhesion is rated as 1 according to the rating standard, which indicates that the plating adhesion on the surface of the tin plate is strong.

Fig. 8 is a schematic view showing the microscopic morphology of the tin-iron alloy layer in the surface plating layer of the tin plate obtained in example 4 of the present application, and it can be seen from fig. 8 that the microscopic morphology of the tin-iron alloy layer in the surface plating layer of the tin plate on the surface of the tin plate obtained in example 4 grows in a columnar shape.

Fig. 9 is a schematic view of the results of the coating adhesion experiment of the tin plate surface coating obtained in example 4 of the present application, and it can be seen from fig. 9 that no tin oxide and chromium oxide are detected on the surface of the stripping tape, and the adhesion reaches level 1 according to the rating standard, indicating that the coating adhesion on the surface of the tin plate is strong.

It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, 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. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.