Electroplating solution, alloy plating layer and preparation method and product thereof

Abstract

The present application relates to an electroplating solution, an alloy coating, and a preparation method and product thereof. The electroplating solution comprises the following components: 260 g / L to 340 g / L of alkali metal pyrophosphate, 15 g / L to 25 g / L of stannous salt, 22 g / L to 30 g / L of cobalt salt, and 5 g / L to 8 g / L of positively charged two-dimensional inorganic nanomaterials. In the electroplating solution, the positively charged two-dimensional inorganic nanomaterials will be adsorbed on the cathode workpiece during the electrodeposition process, and will be deposited together with the metal ions to form a coating and arranged laterally, which can effectively prevent the coating from being eroded, thereby improving the corrosion resistance of the coating. And by controlling the amount of the added positively charged two-dimensional inorganic nanomaterial, the appearance of the tin-cobalt alloy coating is less affected, and the deposited coating has a gray appearance. Therefore, the coating deposited by the electroplating solution has good corrosion resistance while having a gray appearance.

Description

Technical Field

[0001] The present application relates to the field of electroplating, and in particular to an electroplating solution, an alloy coating, and a preparation method and product thereof. Background Art

[0002] With the development of science and technology and the progress of human society, bathroom and home products tend to be more diverse in appearance. Compared with the bright silver-white products, gray series products are becoming more and more popular with consumers. At present, the electrodeposition of tin-cobalt alloy can achieve the deposition of gray coating. However, the tin-cobalt alloy coating only plays a decorative role and cannot achieve corrosion resistance and other properties. It cannot be used directly in products and requires an additional layer of transparent organic protective coating, which is generally obtained by electrophoresis or electrostatic spraying. This method not only increases the process and cost, but also has the risk of falling off due to poor adhesion between the organic protective coating and the inorganic tin-cobalt coating. Summary of the invention

[0003] Based on this, the present application provides an electroplating solution on one hand, and the deposited coating not only has a gray appearance but also has corrosion resistance.

[0004] In addition, another aspect of the present application also provides an alloy coating and a preparation method and product thereof.

[0005] An electroplating solution comprises the following components: 260 g / L to 340 g / L of alkali metal pyrophosphate, 15 g / L to 25 g / L of stannous salt, 22 g / L to 30 g / L of cobalt salt and 5 g / L to 8 g / L of positively charged two-dimensional inorganic nanomaterial.

[0006] Optionally, the two-dimensional inorganic nanomaterial includes one or more of graphene, graphene oxide, carbon nitride, boron nitride and molybdenum disulfide.

[0007] Optionally, the positively charged two-dimensional inorganic nanomaterial is prepared by the following steps:

[0008] The quaternary ammonium salt and the two-dimensional inorganic nanomaterial are mixed in a solvent and ultrasonically dispersed to prepare the two-dimensional inorganic nanomaterial with positive charge.

[0009] Optionally, the quaternary ammonium salt includes one or more of dodecyldimethylbenzylammonium chloride, dioctadecyldimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, cocamidopropyltrimethylammonium chloride and palmitamidopropyltrimethylammonium chloride.

[0010] Optionally, the mass ratio of the quaternary ammonium salt to the two-dimensional inorganic nanomaterial is 1:(1-3).

[0011] Optionally, the solvent comprises anhydrous ethanol.

[0012] Optionally, the electroplating solution further includes 2 g / L to 6 g / L of a third metal salt, and the third metal salt includes one or more of a nickel salt, a copper salt and a zinc salt.

[0013] Optionally, the third metal salt includes one or more of nickel chloride, nickel sulfate, copper chloride, copper sulfate, zinc chloride and zinc sulfate.

[0014] Optionally, the alkali metal pyrophosphate comprises potassium pyrophosphate.

[0015] Optionally, the stannous salt includes one or more of stannous pyrophosphate, stannous sulfate and stannous chloride. Optionally, the stannous salt includes stannous pyrophosphate.

[0016] Optionally, the cobalt salt includes one or more of cobalt chloride, cobalt sulfate and cobalt pyrophosphate. Optionally, the cobalt salt includes cobalt chloride.

[0017] Optionally, the electroplating solution further comprises 15 g / L to 30 g / L of an auxiliary complexing agent, wherein the auxiliary complexing agent comprises one or more of potassium sodium tartrate, sodium citrate, sodium acetate and sodium oxalate. Optionally, the auxiliary complexing agent comprises potassium sodium tartrate.

[0018] Optionally, the electroplating solution further includes 6 g / L to 15 g / L of a conductive agent, wherein the conductive agent includes one or more of ammonium chloride, potassium chloride and sodium chloride. Optionally, the conductive agent includes ammonium chloride.

[0019] Optionally, the electroplating solution further includes 0.5 g / L to 3.5 g / L of a brightener, and optionally, the brightener includes sodium saccharin.

[0020] Optionally, the pH of the electroplating solution is 8-10.

[0021] Optionally, the electroplating solution includes the following components: 270g / L~290g / L potassium pyrophosphate, 18g / L~22g / L stannous pyrophosphate, 24g / L~28g / L cobalt chloride, 4g / L~6g / L third metal salt, 18g / L~22g / L potassium sodium tartrate, 7g / L~11g / L ammonium chloride, 1.5g / L~2.5g / L sodium saccharin and 5g / L~7g / L positively charged two-dimensional inorganic nanomaterial; the third metal salt includes one or more of nickel chloride, copper chloride and zinc chloride.

[0022] Optionally, the electroplating solution includes the following components: 275g / L~285g / L potassium pyrophosphate, 19g / L~21g / L stannous pyrophosphate, 25g / L~27g / L cobalt chloride, 4g / L~6g / L third metal salt, 19g / L~21g / L potassium sodium tartrate, 8g / L~10g / L ammonium chloride, 1.5g / L~2.5g / L sodium saccharin and 5g / L~7g / L positively charged two-dimensional inorganic nanomaterial.

[0023] Optionally, the electroplating solution includes the following components: 280 g / L potassium pyrophosphate, 20 g / L stannous pyrophosphate, 26 g / L cobalt chloride, 5 g / L third metal salt, 20 g / L potassium sodium tartrate, 9 g / L ammonium chloride, 2 g / L sodium saccharin and 6 g / L positively charged two-dimensional inorganic nanomaterial.

[0024] An alloy plating layer is obtained by electroplating with the above-mentioned electroplating solution.

[0025] Optionally, the alloy coating is one of a tin-cobalt-nickel alloy coating, a tin-cobalt-copper alloy coating and a tin-cobalt-zinc alloy coating. Taking the total mass fraction of tin, cobalt and the third metal in the alloy coating as 100%, the mass fraction of tin is 35%~40%, the mass fraction of cobalt is 55%~60%, and the mass fraction of the third metal is 2%~5%, and the third metal is nickel, copper or zinc.

[0026] Optionally, the thickness of the alloy coating is 0.2 μm to 0.5 μm.

[0027] A method for preparing an alloy coating comprises the following steps:

[0028] Obtaining the above-mentioned electroplating solution;

[0029] The electroplating solution is used to electroplate on the surface of a substrate to prepare an alloy plating layer.

[0030] Optionally, the current density during the electroplating process is 2A / dm 2 ~5A / dm 2 The electroplating time is 5min~10min, and the reaction temperature is 45℃~55℃.

[0031] Optionally, before the step of electroplating the substrate surface with the electroplating solution, the step further includes sequentially electroplating a copper layer and a nickel layer on the substrate surface, wherein the alloy coating is formed on a side of the nickel layer away from the substrate.

[0032] A product comprises a substrate and an alloy coating arranged on the surface of the substrate, wherein the alloy coating is prepared as described above or by the preparation method described above.

[0033] Optionally, the product is a kitchen and bathroom hardware product.

[0034] The above-mentioned electroplating solution includes alkali metal pyrophosphate, stannous salt, cobalt salt and positively charged two-dimensional inorganic nanomaterials. Alkali metal pyrophosphate is the main component of the electroplating solution, which serves as the main complexing agent and conductive salt. Stannous salt and cobalt salt provide stannous ions and cobalt ions respectively. The positively charged two-dimensional inorganic nanomaterials will be adsorbed on the cathode workpiece during the electrodeposition process, and will be deposited together with the metal ions to form a coating and arranged laterally, which can effectively prevent the coating from being eroded, thereby improving the corrosion resistance of the coating. And by controlling the amount of the added positively charged two-dimensional inorganic nanomaterial, the appearance of the tin-cobalt alloy coating is less affected, and the deposited coating has a gray appearance. Therefore, the coating deposited by the above-mentioned electroplating solution has good corrosion resistance while having a gray appearance. DETAILED DESCRIPTION

[0035] In order to facilitate the understanding of the present application, the present application will be described more comprehensively below in conjunction with the specific embodiments. The preferred embodiments of the present application are provided in the specific embodiments. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present application belongs. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0037] Unless otherwise specified or there is a contradiction, the terms and phrases used in this application have the following meanings:

[0038] In this application, "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features.

[0039] In the description of the present application, “plurality” means at least two, for example, two, three, etc., unless otherwise clearly and specifically defined.

[0040] In this application, "one or several" refers to any one, any two or more of the listed items. Among them, "several" refers to any two or more of the listed items.

[0041] In this application, the percentage concentration involved, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0042] In this document, "further", "further", "particularly", "for example", "such as", "example", "for example", etc. are used for descriptive purposes, indicating that the previous and subsequent technical solutions are related in terms of the content covered, but should not be understood as a limitation on the previous technical solution, nor can it be understood as a limitation on the protection scope of this document. In this document, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0043] Herein, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel schemes of "yes" or "no". If multiple "optional" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" item is independent of each other. In this application, descriptions such as "optionally contain", "optionally include", etc. mean "contain or not contain". "Optional component X" means that component X exists or does not exist, or means that component X is contained or not contained.

[0044] When a numerical range is disclosed in this application, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed in this application should be understood to include any and all subranges included therein.

[0045] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0046] The terms "including" and "having" and any variations thereof in the embodiments of the present application are intended to cover non-exclusive inclusions. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units that are not listed, or may optionally include other steps or components that are inherent to these processes, methods, products, or devices.

[0047] Reference to "embodiments" in this application means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described in this application may be combined with other embodiments.

[0048] The first aspect of the present application provides an electroplating solution comprising the following components: 260 g / L~340 g / L of alkali metal pyrophosphate, 15 g / L~25 g / L of stannous salt, 22 g / L~30 g / L of cobalt salt and 5 g / L~8 g / L of positively charged two-dimensional inorganic nanomaterial.

[0049] The above-mentioned electroplating solution includes alkali metal pyrophosphate, stannous salt, cobalt salt and positively charged two-dimensional inorganic nanomaterials. Alkali metal pyrophosphate is the main component of the electroplating solution, which serves as the main complexing agent and conductive salt. Stannous salt and cobalt salt provide stannous ions and cobalt ions respectively. The positively charged two-dimensional inorganic nanomaterials will be adsorbed on the cathode workpiece during the electrodeposition process, and will be deposited together with the metal ions to form a coating and arranged laterally, which can effectively prevent the coating from being eroded, thereby improving the corrosion resistance of the coating. And by controlling the amount of the added positively charged two-dimensional inorganic nanomaterial, the appearance of the tin-cobalt alloy coating is less affected, and the deposited coating has a gray appearance. Therefore, the coating deposited by the above-mentioned electroplating solution has good corrosion resistance while having a gray appearance.

[0050] There are mainly the following types of tin-cobalt alloy plating solutions: fluoride system, organic phosphonate system and pyrophosphate system. Fluoride plating solution is highly toxic and has certain difficulties in equipment maintenance and waste liquid treatment. The alloy coating obtained in the organic phosphonate plating solution is prone to cracking and has a short service life. The pyrophosphate system plating solution is non-toxic and non-corrosive, has a low total metal concentration, and is simple to treat wastewater. Therefore, in some embodiments of the present application, the plating solution adopts a pyrophosphate system.

[0051] In some embodiments, the alkali metal pyrophosphate includes one or both of potassium pyrophosphate and sodium pyrophosphate. In one example, the alkali metal pyrophosphate includes potassium pyrophosphate. Specifically, in the plating solution, the concentration of the alkali metal pyrophosphate can be, but is not limited to, 260 g / L, 270 g / L, 280 g / L, 290 g / L, 300 g / L, 310 g / L, 320 g / L, 340 g / L or a range consisting of any two of these values. Optionally, the concentration of the alkali metal pyrophosphate is 270 g / L to 290 g / L. Further optionally, the concentration of the alkali metal pyrophosphate is 275 g / L to 285 g / L.

[0052] In some embodiments, the stannous salt includes one or more of stannous pyrophosphate, stannous sulfate and stannous chloride. In one example, the stannous salt includes stannous pyrophosphate. Specifically, in the electroplating solution, the concentration of the stannous salt can be, but is not limited to, 15g / L, 16g / L, 18g / L, 20g / L, 22g / L, 24g / L, 25g / L or a range consisting of any two of these values. Optionally, the concentration of the stannous salt is 18g / L~22g / L. Further optionally, the concentration of the stannous salt is 19g / L~21g / L.

[0053] In some embodiments, the cobalt salt includes one or more of cobalt pyrophosphate, cobalt sulfate and cobalt chloride. In one example, the cobalt salt includes cobalt chloride. Specifically, in the electroplating solution, the concentration of the cobalt salt can be, but is not limited to, 22 g / L, 24 g / L, 25 g / L, 26 g / L, 28 g / L, 30 g / L or a range consisting of any two of these values. Optionally, the concentration of the cobalt salt is 24 g / L to 28 g / L. Further optionally, the concentration of the cobalt salt is 25 g / L to 27 g / L.

[0054] In some embodiments, the two-dimensional inorganic nanomaterial includes one or more of graphene, graphene oxide, carbon nitride (C3N4), boron nitride and molybdenum disulfide.

[0055] In some embodiments, the positively charged two-dimensional inorganic nanomaterial is prepared by the following steps:

[0056] The quaternary ammonium salt and the two-dimensional inorganic nanomaterial are mixed in a solvent and ultrasonically dispersed to prepare the two-dimensional inorganic nanomaterial with positive charge.

[0057] Specifically, the quaternary ammonium salt includes one or more of dodecyldimethylbenzylammonium chloride, dioctadecyldimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, cocamidopropyltrimethylammonium chloride and palmitamidopropyltrimethylammonium chloride.

[0058] Specifically, the solvent includes anhydrous ethanol.

[0059] Specifically, the mass ratio of the quaternary ammonium salt to the two-dimensional inorganic nanomaterial is 1:(1-3). For example, the mass ratio of the quaternary ammonium salt to the two-dimensional inorganic nanomaterial can be, but is not limited to, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3 or a range consisting of any two of these values.

[0060] Specifically, the ultrasonic dispersion time is 1 h to 2 h.

[0061] Specifically, after the ultrasonic dispersion step, a solvent removal step is also included, for example, by rotary evaporation.

[0062] Specifically, in the electroplating solution, the concentration of the positively charged two-dimensional inorganic nanomaterial can be, but is not limited to, 5 g / L, 6 g / L, 7 g / L, 8 g / L, or a range consisting of any two of these values. Optionally, the concentration of the positively charged two-dimensional inorganic nanomaterial is 5 g / L to 7 g / L.

[0063] The positively charged two-dimensional inorganic nanomaterials form a coating with electrodeposition, and the positively charged two-dimensional inorganic nanomaterials are arranged horizontally, which can effectively prevent the coating from being corroded, thereby improving the corrosion resistance of the coating. Using quaternary ammonium salts to modify two-dimensional inorganic nanomaterials can, on the one hand, make the two-dimensional inorganic nanomaterials positively charged, and on the other hand, it can also improve the dispersibility, stability and antibacterial activity of the electroplating solution.

[0064] In some embodiments, the electroplating solution further includes: a third metal salt of 2 g / L to 6 g / L, and the third metal salt includes one or more of a nickel salt, a copper salt, and a zinc salt. The third metal salt can provide a third metal for the coating, giving the coating a long-lasting broad-spectrum antibacterial property. Specifically, in the electroplating solution, the concentration of the third metal salt can be, but is not limited to, 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, or a range consisting of any two of these values. Optionally, the concentration of the third metal salt is 4 g / L to 6 g / L.

[0065] Specifically, the third metal salt includes one or more of nickel chloride, nickel sulfate, copper chloride, copper sulfate, zinc chloride and zinc sulfate. Optionally, the third metal salt includes one or more of nickel chloride, copper chloride and zinc chloride.

[0066] Specifically, the electroplating solution includes the following components: 260g / L~340g / L of alkali metal pyrophosphate, 15g / L~25g / L of stannous salt, 22g / L~30g / L of cobalt salt, 2g / L~6g / L of third metal salt and 5g / L~8g / L of positively charged two-dimensional inorganic nanomaterial.

[0067] It is understandable that the electroplating solution may also include some additives, such as one or more of an auxiliary complexing agent, a conductive agent and a brightener.

[0068] In some embodiments, the electroplating solution further includes 15 g / L to 30 g / L of an auxiliary complexing agent. For example, in the electroplating solution, the concentration of the auxiliary complexing agent can be, but is not limited to, 15 g / L, 16 g / L, 18 g / L, 20 g / L, 22 g / L, 24 g / L, 25 g / L, 26 g / L, 28 g / L, 30 g / L or a range consisting of any two of these values. Optionally, the concentration of the auxiliary complexing agent is 18 g / L to 22 g / L. Further, the concentration of the auxiliary complexing agent is 19 g / L to 21 g / L.

[0069] Specifically, the auxiliary complexing agent includes one or more of potassium sodium tartrate, sodium citrate, sodium acetate and sodium oxalate. In one example, the auxiliary complexing agent includes potassium sodium tartrate.

[0070] In some embodiments, the electroplating solution further includes 6 g / L to 15 g / L of a conductive agent. For example, in the electroplating solution, the concentration of the conductive agent may be, but is not limited to, 6 g / L, 8 g / L, 10 g / L, 12 g / L, 14 g / L, 15 g / L, or a range consisting of any two of these values. Optionally, the concentration of the conductive agent is 7 g / L to 11 g / L. Further, the concentration of the conductive agent is 8 g / L to 10 g / L.

[0071] Specifically, the conductive agent includes one or more of ammonium chloride, potassium chloride and sodium chloride. In one example, the conductive agent includes ammonium chloride.

[0072] In some embodiments, the electroplating solution further includes a brightener of 0.5 g / L to 3.5 g / L. For example, in the electroplating solution, the concentration of the brightener may be, but is not limited to, 0.5 g / L, 0.8 g / L, 1 g / L, 1.2 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 2.2 g / L, 2.5 g / L, 3 g / L, 3.5 g / L, or a range consisting of any two of these values. Optionally, the concentration of the brightener is 1.5 g / L to 2.5 g / L. Specifically, the brightener includes sodium saccharin.

[0073] In some embodiments, the stannous salt includes stannous pyrophosphate, and the cobalt salt includes cobalt chloride. The electroplating solution formed by combining stannous pyrophosphate and cobalt chloride has better stability, better electroplating uniformity, and a wider range of applications.

[0074] In some embodiments, the electroplating solution includes the following components: 260 g / L~340 g / L potassium pyrophosphate, 15 g / L~25 g / L stannous pyrophosphate, 22 g / L~30 g / L cobalt chloride, 2 g / L~6 g / L third metal salt, 15 g / L~30 g / L potassium sodium tartrate, 6 g / L~15 g / L ammonium chloride, 0.5 g / L~3.5 g / L saccharin sodium and 5 g / L~8 g / L positively charged two-dimensional inorganic nanomaterials.

[0075] In some embodiments, the pH of the plating solution is 8-10.

[0076] Optionally, in some embodiments, the electroplating solution includes the following components: 270 g / L~290 g / L potassium pyrophosphate, 18 g / L~22 g / L stannous pyrophosphate, 24 g / L~28 g / L cobalt chloride, 4 g / L~6 g / L third metal salt, 18 g / L~22 g / L potassium sodium tartrate, 7 g / L~11 g / L ammonium chloride, 1.5 g / L~2.5 g / L sodium saccharin and 5 g / L~7 g / L positively charged two-dimensional inorganic nanomaterials.

[0077] Optionally, in some embodiments, the electroplating solution includes the following components: 275 g / L~285 g / L potassium pyrophosphate, 19 g / L~21 g / L stannous pyrophosphate, 25 g / L~27 g / L cobalt chloride, 4 g / L~6 g / L third metal salt, 19 g / L~21 g / L potassium sodium tartrate, 8 g / L~10 g / L ammonium chloride, 1.5 g / L~2.5 g / L sodium saccharin and 5 g / L~7 g / L positively charged two-dimensional inorganic nanomaterials.

[0078] Optionally, in some embodiments, the electroplating solution includes the following components: 280 g / L potassium pyrophosphate, 20 g / L stannous pyrophosphate, 26 g / L cobalt chloride, 5 g / L third metal salt, 20 g / L potassium sodium tartrate, 9 g / L ammonium chloride, 2 g / L sodium saccharin and 6 g / L positively charged two-dimensional inorganic nanomaterial.

[0079] A second aspect of the present application provides an alloy plating layer obtained by electroplating using the electroplating solution of the first aspect.

[0080] In some embodiments, the alloy plating layer is one of a tin-cobalt-nickel alloy plating layer, a tin-cobalt-copper alloy plating layer, and a tin-cobalt-zinc alloy plating layer.

[0081] In some embodiments, taking the total mass fraction of tin, cobalt and the third metal in the alloy coating as 100%, the mass fraction of tin is 35% to 40%, the mass fraction of cobalt is 55% to 60%, the mass fraction of the third metal is 2% to 5%, and the third metal is nickel, copper or zinc. For example, the mass fraction of tin can be, but is not limited to, 35%, 36%, 37%, 38%, 39%, 40% or a range consisting of any two of these values. The mass fraction of cobalt can be, but is not limited to, 55%, 56%, 57%, 58%, 59%, 60% or a range consisting of any two of these values. The mass fraction of the third metal can be, but is not limited to, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or a range consisting of any two of these values.

[0082] In some embodiments, the thickness of the alloy coating is 0.2 μm to 0.5 μm.

[0083] The alloy coating has a grey appearance and also has good antibacterial and corrosion resistance.

[0084] The third aspect of the present application also provides a method for preparing an alloy coating, comprising the following steps:

[0085] Obtaining the above-mentioned electroplating solution;

[0086] The alloy coating is prepared by electroplating the surface of the substrate with an electroplating solution.

[0087] In some embodiments, the thickness of the alloy coating is 0.2 μm to 0.5 μm.

[0088] In some embodiments, the current density during the electroplating process is 2A / dm 2 ~5A / dm 2 , the electroplating time is 5min~10min, and the reaction temperature is 45℃~55℃. Specifically, during the electroplating process, graphite is used as the anode, the substrate to be plated is the cathode, and the anode and cathode are kept parallel.

[0089] In some embodiments, the substrate includes one or more of copper alloy, zinc alloy, stainless steel and aluminum alloy. It is understood that only several common substrates are given above, but they are not limited thereto.

[0090] In some embodiments, the step of pre-treating the substrate is also included. The substrate pre-treatment refers to cleaning the substrate through an electroplating cleaning line to remove grease, dirt, etc. on the surface of the substrate. This process is relatively common and will not be described in detail. For example, the substrate is subjected to at least one of dewaxing, degreasing, electrolysis and pure water cleaning.

[0091] In some embodiments, before the step of electroplating the substrate surface with an electroplating solution, a step of electroplating a copper layer and a nickel layer on the substrate surface is also included, and the alloy plating layer is formed on the side of the nickel layer away from the substrate.

[0092] In some embodiments, in the step of electroplating the copper layer, the pre-treated substrate is placed in a copper electroplating solution to deposit the copper layer.

[0093] Specifically, the copper layer includes two or more of a base copper layer, a copper pyrophosphate layer and a copper sulfate layer. For specific copper electroplating solution and electroplating process, reference can be made to the copper electroplating part in the patent "CN201911282514.X A discoloration-resistant matte black chromium composite coating and its preparation method".

[0094] Specifically, the total thickness of the copper layer is 15 μm to 20 μm.

[0095] In some embodiments, in the step of electroplating the nickel layer, the copper-plated substrate is placed in a nickel electroplating solution to deposit the nickel layer.

[0096] Specifically, the nickel layer includes two or more of an impact nickel layer, a semi-bright nickel layer, a full-bright nickel layer and a high-sulfur nickel layer. For specific nickel electroplating solutions and electroplating processes, reference can be made to the nickel electroplating section in the patent "CN202010681548.2 An antibacterial black chromium surface coating and its preparation method".

[0097] Specifically, the total thickness of the nickel layer is 15 μm to 20 μm.

[0098] Before electroplating the alloy layer, copper layer and nickel layer are electroplated first. The copper layer is beneficial to improving the flatness and bonding strength with the substrate, and the nickel layer is beneficial to improving the corrosion resistance.

[0099] The fourth aspect of the present application provides a product, comprising a substrate and an alloy coating disposed on the surface of the substrate, wherein the alloy coating is prepared as described in the second aspect or by the preparation method of the third aspect.

[0100] In some embodiments, the product is a kitchen and bathroom hardware product, for example, a shower head, a faucet, a shower column, etc.

[0101] In order to make the purpose and advantages of the present application clearer, the electroplating solution, alloy coating and its effect of the present application are further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and shall not be used to limit the present application. The following embodiments do not include other components except inevitable impurities unless otherwise specified. The drugs and instruments used in the embodiments are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the embodiments are implemented according to conventional conditions, such as the conditions described in the literature and books or the methods recommended by the manufacturer.

[0102] Example 1

[0103] The present embodiment provides an electroplating solution, comprising the following components: 280 g / L potassium pyrophosphate, 20 g / L stannous pyrophosphate, 26 g / L cobalt chloride, 5 g / L nickel chloride, 20 g / L potassium sodium tartrate, 9 g / L ammonium chloride, 2 g / L sodium saccharin, and 6 g / L graphene modified with dodecyltrimethylammonium chloride, with a pH of 8.5. The graphene modified with dodecyltrimethylammonium chloride is obtained by the following steps: dodecyltrimethylammonium chloride and graphene are mixed in anhydrous ethanol, ultrasonically dispersed for 1.5 hours, and then the anhydrous ethanol is removed by a rotary evaporator to obtain graphene modified with dodecyltrimethylammonium chloride, and the mass percentage concentration of dodecyltrimethylammonium chloride and graphene in anhydrous ethanol is 10%.

[0104] This embodiment also provides a method for preparing an alloy coating, comprising the following steps:

[0105] (1) Pre-treat the substrate to remove grease, dirt, etc. on the surface of the substrate.

[0106] (2) Electroplating a copper layer on the pre-treated substrate, wherein the copper layer includes a base copper layer and a copper sulfate layer. For specific processes, refer to the copper electroplating part in "CN201911282514.X A discoloration-resistant matte black chromium composite coating and its preparation method".

[0107] (3) Electroplating a nickel layer on the copper-plated substrate, wherein the nickel layer includes a semi-bright nickel layer and a full-bright nickel layer. For the specific process, refer to the nickel electroplating part in "CN202010681548.2 An antibacterial black chromium surface coating and its preparation method".

[0108] (4) Electroplating the nickel-plated substrate with the above-mentioned electroplating solution, the electroplating process is set as follows: graphite is the anode, the workpiece to be plated is the cathode, and the anode and cathode are kept parallel, and the current density is 2.5A / dm 2 , the electroplating time is 5 min, the reaction temperature is 55 ° C, and an alloy coating is obtained.

[0109] Embodiment 2 to Embodiment 5

[0110] Embodiments 2 to 5 provide a plating solution, each having a composition similar to that of the plating solution of Embodiment 1, except that the composition of the third metal salt and the corrosion inhibitor are different, as shown in Table 1 below.

[0111] The preparation method of the alloy coating of Examples 2 to 5 is the same as that of Example 1 and will not be described in detail.

[0112] Example 6

[0113] This embodiment provides an electroplating solution, which is similar in composition to the electroplating solution of embodiment 3, except that no third metal salt is added. The specific composition is shown in Table 2 below.

[0114] The preparation method of the alloy coating of this embodiment is the same as that of Embodiment 3 and will not be described in detail.

[0115] Example 7

[0116] This embodiment provides an electroplating solution, which is similar in composition to the electroplating solution of embodiment 3, except that the concentration of the third metal salt nickel chloride is different. The specific composition is shown in Table 2 below.

[0117] The preparation method of the alloy coating of this embodiment is the same as that of Embodiment 3 and will not be described in detail.

[0118] Comparative Example 1

[0119] Comparative Example 1 provides an electroplating solution, which is similar in composition to the electroplating solution of Example 3, except that no positively charged two-dimensional inorganic nanomaterial is added. The specific composition is shown in Table 2 below.

[0120] The preparation method of the alloy coating of Comparative Example 1 is the same as that of Example 3 and will not be described in detail.

[0121] Comparative Example 2

[0122] Comparative Example 2 provides an electroplating solution, which is similar in composition to the electroplating solution of Example 3, except that the concentration of the positively charged two-dimensional inorganic nanomaterial is different. The specific composition is shown in Table 2 below.

[0123] The preparation method of the alloy coating of Comparative Example 2 is the same as that of Example 3 and will not be described in detail.

[0124] Table 1 Composition of the plating solution and the plating process of the embodiment

[0125]

[0126] Table 2 Composition of the electroplating solution and electroplating process of each embodiment and comparative example

[0127]

[0128] The alloy coatings of the above-mentioned embodiments and comparative examples were subjected to the Escherichia coli antibacterial rate, Staphylococcus aureus antibacterial rate and acetic acid salt spray test (AASS), and the experimental data shown in Table 3 were obtained. The test standards for the Escherichia coli antibacterial rate and Staphylococcus aureus antibacterial rate are GB / T 21866-2008 Antibacterial performance and antibacterial effect of antibacterial coatings (paint films), and the test standard for the acetic acid salt spray test is GB / T 10125-2021 Artificial atmosphere corrosion test salt spray test standard.

[0129] Table 3 Performance comparison of examples and comparative examples

[0130]

[0131] As can be seen from Table 3 above, the electroplating solution of the comparative example does not contain positively charged two-dimensional inorganic nanomaterials or the amount thereof is too large, and slight corrosion occurs after 48 hours of salt spray test. In addition, by adding a certain amount of the third metal salt to the electroplating solution, it is beneficial to improve the antibacterial property of the coating, so that the coating has good corrosion resistance and good antibacterial property. In addition, the amount of positively charged two-dimensional inorganic nanomaterials in the electroplating solution of Comparative Example 2 is too large, which will also affect the appearance of the coating.

[0132] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0133] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the protection scope of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. An electroplating solution, characterized in that: The invention comprises the following components: 260g / L~340g / L of alkali metal pyrophosphate, 15g / L~25g / L of stannous salt, 22g / L~30g / L of cobalt salt and 5g / L~8g / L of positively charged two-dimensional inorganic nanomaterial.

2. The electroplating solution according to claim 1, characterized in that The two-dimensional inorganic nanomaterial includes one or more of graphene, graphene oxide, carbon nitride, boron nitride and molybdenum disulfide.

3. The electroplating solution according to claim 1 or 2, characterized in that: The positively charged two-dimensional inorganic nanomaterial is prepared by the following steps: The quaternary ammonium salt and the two-dimensional inorganic nanomaterial are mixed in a solvent and ultrasonically dispersed to prepare the two-dimensional inorganic nanomaterial with positive charge; Optionally, the quaternary ammonium salt includes one or more of dodecyldimethylbenzylammonium chloride, dioctadecyldimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, cocamidopropyltrimethylammonium chloride and palmitamidopropyltrimethylammonium chloride; Optionally, the mass ratio of the quaternary ammonium salt to the two-dimensional inorganic nanomaterial is 1:(1-3).

4. The electroplating solution according to claim 1, characterized in that The electroplating solution further includes 2 g / L to 6 g / L of a third metal salt, wherein the third metal salt includes one or more of a nickel salt, a copper salt and a zinc salt; Optionally, the third metal salt includes one or more of nickel chloride, nickel sulfate, copper chloride, copper sulfate, zinc chloride and zinc sulfate.

5. The electroplating solution according to claim 1, 2 or 4, characterized in that: Meet one or more of the following conditions: (1) The alkali metal pyrophosphate includes potassium pyrophosphate; (2) The stannous salt includes one or more of stannous pyrophosphate, stannous sulfate and stannous chloride. Optionally, the stannous salt includes stannous pyrophosphate; (3) The cobalt salt includes one or more of cobalt chloride, cobalt sulfate and cobalt pyrophosphate. Optionally, the cobalt salt includes cobalt chloride; (4) The electroplating solution further includes 15 g / L to 30 g / L of an auxiliary complexing agent, wherein the auxiliary complexing agent includes one or more of potassium sodium tartrate, sodium citrate, sodium acetate and sodium oxalate. Optionally, the auxiliary complexing agent includes potassium sodium tartrate; (5) The electroplating solution further includes 6 g / L to 15 g / L of a conductive agent, wherein the conductive agent includes one or more of ammonium chloride, potassium chloride and sodium chloride. Optionally, the conductive agent includes ammonium chloride; (6) The electroplating solution further comprises 0.5 g / L to 3.5 g / L of a brightener, and optionally, the brightener comprises sodium saccharin; (7) The pH of the electroplating solution is 8-10.

6. The electroplating solution according to claim 5, characterized in that The electroplating solution comprises the following components: 270 g / L to 290 g / L potassium pyrophosphate, 18 g / L to 22 g / L stannous pyrophosphate, 24 g / L to 28 g / L cobalt chloride, 4 g / L to 6 g / L third metal salt, 18 g / L to 22 g / L potassium sodium tartrate, 7 g / L to 11 g / L ammonium chloride, 1.5 g / L to 2.5 g / L sodium saccharin and 5 g / L to 7 g / L positively charged two-dimensional inorganic nanomaterial; the third metal salt comprises one or more of nickel chloride, copper chloride and zinc chloride; Optionally, the electroplating solution includes the following components: 275 g / L to 285 g / L potassium pyrophosphate, 19 g / L to 21 g / L stannous pyrophosphate, 25 g / L to 27 g / L cobalt chloride, 4 g / L to 6 g / L third metal salt, 19 g / L to 21 g / L potassium sodium tartrate, 8 g / L to 10 g / L ammonium chloride, 1.5 g / L to 2.5 g / L sodium saccharin, and 5 g / L to 7 g / L positively charged two-dimensional inorganic nanomaterials; Optionally, the electroplating solution includes the following components: 280 g / L potassium pyrophosphate, 20 g / L stannous pyrophosphate, 26 g / L cobalt chloride, 5 g / L third metal salt, 20 g / L potassium sodium tartrate, 9 g / L ammonium chloride, 2 g / L sodium saccharin and 6 g / L positively charged two-dimensional inorganic nanomaterial.

7. An alloy coating, characterized in that: The alloy plating layer is obtained by electroplating using the electroplating solution according to any one of claims 1 to 6.

8. The alloy coating according to claim 7, characterized in that: The alloy coating is one of a tin-cobalt-nickel alloy coating, a tin-cobalt-copper alloy coating and a tin-cobalt-zinc alloy coating, and taking the total mass fraction of tin, cobalt and a third metal in the alloy coating as 100%, the mass fraction of tin is 35% to 40%, the mass fraction of cobalt is 55% to 60%, and the mass fraction of the third metal is 2% to 5%, and the third metal is nickel, copper or zinc; and / or, The thickness of the alloy coating is 0.2 μm to 0.5 μm.

9. A method for preparing an alloy coating, characterized in that: The steps include: Obtaining the electroplating solution according to any one of claims 1 to 6; The electroplating solution is used to electroplate on the surface of a substrate to prepare an alloy plating layer.

10. The method for preparing the alloy coating according to claim 9, characterized in that: The current density during electroplating is 2A / dm 2 ~5A / dm 2 , the electroplating time is 5min~10min, the reaction temperature is 45℃~55℃; and / or, Before the step of electroplating the substrate surface with the electroplating solution, the method further includes the step of sequentially electroplating a copper layer and a nickel layer on the substrate surface, wherein the alloy plating layer is formed on the side of the nickel layer away from the substrate.

11. A product, characterized in that Comprising a substrate and an alloy coating disposed on the surface of the substrate, wherein the alloy coating is as described in any one of claims 7 to 8 or is prepared by the preparation method as described in any one of claims 9 to 10; Optionally, the product is a kitchen and bathroom hardware product.

Images