Composite electroplating solution, hydrophobic electroplating coating, preparation method thereof, and electroplating products

Abstract

This invention discloses a composite electroplating solution, a hydrophobic electroplating coating, a preparation method thereof, and an electroplated product. The composite electroplating solution comprises a solvent, a conductive salt (200 g / L~250 g / L), a plating starter (10 g / L~20 g / L), a wetting agent (0.5 mL / L~1 mL / L), a trivalent chromium salt (18 g / L~20 g / L), boric acid (60 g / L~80 g / L), composite nanoparticles (1 g / L~2 g / L), and a morphology control agent (20 mg / L~500 mg / L). This composite electroplating solution can be used to prepare hydrophobic electroplating coatings, simplifying the process steps. A one-step process can achieve hydrophobic coating preparation, resulting in high efficiency. The prepared hydrophobic electroplating coating does not contain fluorine-based organic compounds, making it friendly to operators and the environment. Furthermore, the hydrophobic electroplating coating prepared by this composite electroplating solution exhibits an increased water contact angle and improved wear resistance.

Description

Technical Field

[0001] This application relates to the field of electroplating technology, and in particular to a composite electroplating solution, a method for preparing composite nanoparticles, an electroplated hydrophobic coating and its preparation method, and electroplated products. Background Technology

[0002] Currently, the commonly used electroplating process for preparing hydrophobic composite coatings involves two or more steps: first, an electroplated layer is prepared, followed by treatment with a low surface energy solution. This process is complex, inefficient, and fails to meet current needs. Furthermore, existing processes often result in coatings containing fluorinated organic compounds, which pose a pollution risk to workers and the environment. Summary of the Invention

[0003] Therefore, it is necessary to provide a composite electroplating solution. The composite electroplating solution of the present invention can be used to prepare hydrophobic coatings, simplifying the process steps of electroplating hydrophobic coatings. It can achieve the preparation of hydrophobic coatings in a single process, with high preparation efficiency. Moreover, the prepared electroplated hydrophobic coating does not contain fluorine-based organic compounds, which is friendly to operators and the environment.

[0004] One embodiment of this application provides a composite electroplating solution.

[0005] A composite electroplating solution, comprising:

[0006] Solvent;

[0007] Conductive salt concentration: 200g / L~350g / L;

[0008] Starter agent: 10g / L~20g / L;

[0009] Wetting agent: 0.5 mL / L ~ 2 mL / L;

[0010] Trivalent chromium salts: 18g / L~25g / L;

[0011] Boric acid 60g / L~65g / L;

[0012] Composite nanoparticles 1g / L~10g / L; and

[0013] Morphology control agent: 20 mg / L to 500 mg / L.

[0014] In some embodiments, the composite nanoparticles are formed by immersing nanoparticles in a composite solution, wherein the nanoparticles include one or more of silicon particles, silicon dioxide particles, titanium dioxide particles, and aluminum oxide particles.

[0015] In some embodiments, the composite electroplating solution also satisfies at least one of the following conditions:

[0016] (1) The conductive salt includes one or more of sodium chloride, potassium chloride, ammonium chloride, potassium sulfate, and ammonium sulfate;

[0017] (2) The trivalent chromium salt includes one or more of chromium sulfate, chromium chloride, and chromium formate;

[0018] (3) The morphology control agent includes one or two of PEG and Janus Green.

[0019] In some embodiments, the nanoparticles have a particle size of 30 nm to 200 nm.

[0020] In some embodiments, the composite solution comprises the following components: a cationic surfactant, silane, ethanol, water, and an acid, wherein the mass ratio of the cationic surfactant, silane, ethanol, water, and acid is (0.125~2.5):(0.5~5):100:(0.05~0.5):(0.003~0.03), and 1 / 4 ≤ mass of cationic surfactant / mass of silane ≤ 1 / 2.

[0021] In some embodiments, the composite electroplating solution also satisfies at least one of the following conditions:

[0022] (1) The cationic surfactant includes one or more of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and octadecyldimethylbenzylammonium chloride;

[0023] (2) The silane includes one or more of octadecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane;

[0024] (3) The acid includes one or more of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid.

[0025] One embodiment of this application provides a method for preparing composite nanoparticles.

[0026] A method for preparing composite nanoparticles includes the following steps:

[0027] The nanoparticles were pretreated, washed, filtered, and freeze-dried in sequence, then immersed in a composite solution to form an immersion mixture. The immersion mixture was filtered and dried to obtain the composite nanoparticles.

[0028] In some embodiments, the preprocessing includes the following steps:

[0029] The nanoparticles were immersed in a piranha solution for 5 to 20 seconds to remove impurities from the surface of the nanoparticles and to hydroxylate the surface of the nanoparticles.

[0030] In some embodiments, the cleaning and filtration process includes the following steps: cleaning the nanoparticles with pure water at least once.

[0031] In some embodiments, immersion in the composite solution specifically includes the following steps:

[0032] After mixing the nanoparticles with the composite solution, the mixture is soaked for 10 min to 3 h under ultrasonic and stirring conditions; wherein the mass ratio of the nanoparticles to the composite solution is 1:(20~100), and the temperature of the composite solution is controlled at 30℃~55℃.

[0033] In some embodiments, the soaking mixture is filtered and then dried, including the following steps:

[0034] The soaking mixture is filtered and then rinsed with ethanol at least three times; the collected solid particles are baked at 60℃~70℃ for 2h~3h to obtain the composite nanoparticles.

[0035] One embodiment of this application provides a method for preparing an electroplated hydrophobic coating.

[0036] A method for preparing an electroplated hydrophobic coating includes the following steps:

[0037] The composite electroplating solution described above is used to electroplat the substrate to be electroplated, forming a hydrophobic coating on the surface of the substrate.

[0038] In some embodiments, during the electroplating process, at least one of the following parameters is satisfied: the pH value of the composite electroplating solution is controlled to be 3-4, the temperature is controlled to be 45°C-55°C, and the current density is controlled to be 2A / dm³. 2 ~4.5A / dm 2 The electroplating time is 500s~1200s.

[0039] In some embodiments, after the electroplating process is completed, the process further includes cleaning and drying the resulting coating, specifically including the following steps:

[0040] After cleaning the coating with pure water, it is dried at 70℃~120℃.

[0041] One embodiment of this application provides an electroplated hydrophobic coating.

[0042] An electroplated hydrophobic coating is prepared using the preparation method described above. The average initial water contact angle (WCA) of the electroplated hydrophobic coating is 110°~113°. After 10,000 wear resistance tests, the average water contact angle (WCA) of the electroplated hydrophobic coating is 105°~106°.

[0043] One embodiment of this application provides an electroplating product.

[0044] An electroplating product includes an electroplating substrate and an electroplating hydrophobic coating prepared by the above-described preparation method, wherein the electroplating hydrophobic coating is formed on the surface of the electroplating substrate.

[0045] The composite electroplating solution of this application can be used to prepare hydrophobic coatings, simplifying the process steps. It allows for the preparation of hydrophobic coatings in a single step, resulting in high efficiency. Furthermore, the prepared hydrophobic coating does not contain fluorine-based organic compounds, making it environmentally friendly and preventing pollution. Further, the hydrophobic coating prepared with the composite electroplating solution of this application exhibits a significantly improved initial water contact angle and wear resistance. The average initial water contact angle (WCA) of the hydrophobic coating prepared with the composite electroplating solution of this application is 110°~113°, and after 10,000 wear resistance tests, the average water contact angle (WCA) of the hydrophobic coating is 105°~106°. Attached Figure Description

[0046] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0047] To gain a more complete understanding of this application and its beneficial effects, the following description will be provided in conjunction with the accompanying drawings. In the following description, the same reference numerals denote the same parts.

[0048] Figure 1 AFM (Atomic Force Microscopy) image of the electroplated hydrophobic coating prepared in Example 1;

[0049] Figure 2 The image shows the initial water contact angle (WCA) of the electroplated hydrophobic coating prepared in Example 1.

[0050] Figure 3 The image shows a water contact angle (WCA) test photo of the electroplated hydrophobic coating prepared in Example 1 after wear testing.

[0051] Figure 4 AFM image of the electroplated hydrophobic coating prepared in Example 2;

[0052] Figure 5 The image shows the initial water contact angle (WCA) of the electroplated hydrophobic coating prepared in Example 2.

[0053] Figure 6The image shows a water contact angle (WCA) test photo of the electroplated hydrophobic coating prepared in Example 2 after wear testing.

[0054] Figure 7 AFM image of the electroplated hydrophobic coating prepared in Comparative Example 1;

[0055] Figure 8 The image shows the initial water contact angle (WCA) of the electroplated hydrophobic coating prepared in Comparative Example 1.

[0056] Figure 9 The image shows the water contact angle (WCA) of the electroplated hydrophobic coating prepared in Comparative Example 1 after wear testing.

[0057] Figure 10 AFM image of the electroplated hydrophobic coating prepared in Comparative Example 2;

[0058] Figure 11 Photographs of the initial water contact angle (WCA) of the electroplated hydrophobic coating prepared in Comparative Example 2.

[0059] Figure 12 The image shows the water contact angle (WCA) of the electroplated hydrophobic coating prepared in Comparative Example 2 after wear testing. Detailed Implementation

[0060] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0061] In the description of this invention, "several" means one or more, "multiple" means two or more, "greater than," "less than," and "exceeding" are understood to exclude the stated number, while "above," "below," and "within" are understood to include the stated number. The use of "first" and "second" in the description is merely for distinguishing technical features and should not be construed as indicating or implying relative importance, or implicitly indicating the number of indicated technical features, or implicitly indicating the order of the indicated technical features.

[0062] In this invention, unless otherwise stated, the sum of the parts of each component in the composition can be 100 parts by weight. In this application, when referring to numerical ranges (i.e., numerical intervals), unless otherwise specified, the distribution of selectable values ​​within the numerical range is considered continuous, and includes the two endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between these two endpoints. Unless otherwise specified, when a numerical range refers only to integers within the numerical range, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical range can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical range" can broadly include percentage ranges, ratio ranges, proportion ranges, and other quantitative ranges.

[0063] Unless otherwise defined, 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 pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0064] Firstly, embodiments of this application provide a composite electroplating solution to address the problems of existing electroplating hydrophobic coating preparation processes, which involve two or more steps, resulting in complex processes, low preparation efficiency, and difficulty in meeting current needs; and the issue that existing preparation processes often result in coatings containing fluorinated organic compounds, causing pollution to workers and the environment. The composite electroplating solution provided in this application can be used for preparing hydrophobic electroplating coatings.

[0065] A composite electroplating solution includes a solvent, a conductive salt, a plating starter, a wetting agent, a trivalent chromium salt, boric acid, composite nanoparticles, and a morphology control agent. The concentrations of each component are as follows:

[0066] Conductive salt concentration: 200g / L~350g / L;

[0067] Starter agent: 10g / L~20g / L;

[0068] Wetting agent: 0.5 mL / L ~ 2 mL / L;

[0069] Trivalent chromium salts: 18g / L~25g / L;

[0070] Boric acid 60g / L~65g / L;

[0071] Composite nanoparticles 1g / L~10g / L; and

[0072] Morphology control agent: 20 mg / L to 500 mg / L.

[0073] In some embodiments, the composite electroplating solution includes a solvent, a conductive salt, a plating starter, a wetting agent, a trivalent chromium salt, boric acid, composite nanoparticles, and a morphology control agent. The concentrations of each component are as follows:

[0074] Conductive salt 250g / L~300g / L;

[0075] Starter agent: 10g / L~15g / L;

[0076] Wetting agent: 0.5 mL / L ~ 1 mL / L;

[0077] Trivalent chromium salts: 18g / L~20g / L;

[0078] Boric acid 60g / L~70g / L;

[0079] Composite nanoparticles 1g / L~2g / L; and

[0080] Morphology control agent: 20 mg / L to 300 mg / L.

[0081] In some embodiments, the composite nanoparticles are formed by immersing nanoparticles in a composite solution, wherein the nanoparticles include one or more of silicon particles, silicon dioxide particles, titanium dioxide particles, and aluminum oxide particles.

[0082] In some embodiments, the nanoparticles include one or more of silicon particles, silicon dioxide particles, titanium dioxide particles, and aluminum oxide particles.

[0083] In some embodiments, the nanoparticle size is 30 nm to 200 nm. For example, the nanoparticle size includes, but is not limited to, 30 nm, 40 nm, 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 170 nm, 180 nm, 200 nm or any range between the foregoing.

[0084] In some embodiments, the conductive salt includes one or more of sodium chloride, potassium chloride, ammonium chloride, potassium sulfate, and ammonium sulfate.

[0085] In some embodiments, the ignition agent includes one or more of Anmet brand white easy-bright trivalent chromium ignition agent 1687213.

[0086] In some embodiments, the wetting agent includes one or more of Anmet brand white easy-to-bright trivalent chromium wetting agent 1687218.

[0087] In some embodiments, the trivalent chromium salt includes one or more of chromium sulfate, chromium chloride, and chromium formate.

[0088] In some embodiments, the morphology control agent is one or both of PEG (polyethylene glycol) and Janus Green. The number average molecular weight of PEG is 300-5000.

[0089] In some embodiments, the composite solution comprises the following components: cationic surfactant, silane, ethanol, water, and acid, wherein the mass ratio of cationic surfactant, silane, ethanol, water, and acid is (0.125~2.5):(0.5~5):100:(0.05~0.5):(0.003~0.03), and 1 / 4 ≤ cationic surfactant mass / silane mass ≤ 1 / 2, that is, the mass ratio of cationic surfactant to silane is between 0.25 and 0.5. This can control the content of cationic surfactant and silane, avoiding excessive or insufficient content of cationic surfactant or silane, which would reduce the low surface energy composite effect of nanoparticles. For example, the mass ratio of cationic surfactant, silane, ethanol, water, and acid is 0.125:0.5:100:0.05:0.003; another example is a mass ratio of 2.5:5:100:0.5:0.03; yet another example is a mass ratio of 1:2:100:0.1:~0.01. The composite solution composed of these components exhibits low surface energy properties.

[0090] In some embodiments, the cationic surfactant includes one or more of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and octadecyldimethylbenzylammonium chloride.

[0091] In some embodiments, the silane includes one or more of octadecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane.

[0092] In some embodiments, the acid includes one or more of concentrated sulfuric acid, concentrated hydrochloric acid, and concentrated nitric acid.

[0093] In some embodiments, the solvent in the composite electroplating solution may be water.

[0094] The preparation method of the above-mentioned composite nanoparticles includes the following steps:

[0095] The nanoparticles were pretreated, washed, filtered, and freeze-dried in sequence, and then immersed in a composite solution to form an immersion mixture. The immersion mixture was filtered and dried to obtain composite nanoparticles.

[0096] In some embodiments, the pretreatment of nanoparticles includes the following steps:

[0097] Nanoparticles are immersed in a piranha-infused solution for 5 to 20 seconds to remove surface impurities and hydroxylate the nanoparticles. For example, immersion times include, but are not limited to, 5 seconds, 6 seconds, 8 seconds, 10 seconds, 12 seconds, 13 seconds, 15 seconds, 17 seconds, 19 seconds, 20 seconds, or any range between these values. The piranha-infused solution, also known as the piranha etching solution, is a mixture of concentrated sulfuric acid and 30% hydrogen peroxide, with a volume ratio of concentrated sulfuric acid to hydrogen peroxide of 7:3.

[0098] In some embodiments, the pretreatment and subsequent cleaning and filtration of nanoparticles includes the following steps: cleaning and filtering the nanoparticles with pure water at least once.

[0099] In some embodiments, the freeze-drying of nanoparticles after washing and filtration includes the following steps: using a freeze-drying device to dry the nanoparticles to prevent them from agglomerating.

[0100] In some embodiments, immersion in the composite solution specifically includes the following steps:

[0101] After mixing nanoparticles with a composite solution, the mixture is soaked for 10 min to 3 h under ultrasonic and stirring conditions. The mass ratio of nanoparticles to the composite solution is 1:(20~100), and the temperature of the composite solution is controlled at 30℃~55℃. For example, the soaking time may include, but is not limited to: 10 min, 20 min, 30 min, 50 min, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, or any range between the aforementioned values. Similarly, the mass ratio of nanoparticles to the composite solution may include, but is not limited to: 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, or any range between the aforementioned values. Furthermore, the solution temperature may include, but is not limited to: 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, or any range between the aforementioned values. The temperature of the composite solution should not be too high. When the temperature of the composite solution is too high, the hydrolysis rate is too fast, resulting in severe condensation of nanoparticles. The temperature of the composite solution should not be too low. When the temperature of the composite solution is too low, the immersion treatment effect of nanoparticles is not good, which is not conducive to the subsequent electroplating process and results in poor electroplating coating effect.

[0102] In some embodiments, the soaking mixture is filtered and then dried, including the following steps:

[0103] The soaking mixture is filtered and then washed with ethanol at least three times. The collected solid particles are baked at 60℃~70℃ for 2h~3h to obtain composite nanoparticles. The baking temperature includes, but is not limited to, 60℃, 62℃, 63℃, 65℃, 67℃, 70℃, or any range between the aforementioned. The baking time includes, but is not limited to, 2h, 2.5h, 3h, or any range between the aforementioned. The filtration process includes vacuum filtration of the soaking mixture and washing the obtained solid particles with ethanol under reduced pressure of approximately 1~2 bar.

[0104] Secondly, one embodiment of this application provides a method for preparing an electroplated hydrophobic coating.

[0105] In this application, unless otherwise stated, the reaction steps may be performed in the order stated herein or not. For example, other steps may be included between reaction steps, and the order of reaction steps may be appropriately changed. This is something that a person skilled in the art can determine based on conventional knowledge and experience. Preferably, the reaction methods described herein are performed sequentially.

[0106] A method for preparing an electroplated hydrophobic coating includes the following steps:

[0107] The above-mentioned composite electroplating solution is used to electroplat the substrate to be electroplated, forming a hydrophobic coating on the surface of the substrate.

[0108] In some embodiments, during the electroplating process, at least one of the following parameters is satisfied: the pH value of the composite electroplating solution is controlled to be 3-4, the temperature is controlled to be 45°C-55°C, and the current density is 2A / dm³. 2 ~4.5A / dm 2 The electroplating time is 500s to 1200s. For example, the pH value of the composite electroplating solution includes, but is not limited to, 3, 3.2, 3.5, 3.6, 3.8, 4, or any two of the aforementioned values. The electroplating temperature includes, but is not limited to, 45℃, 47℃, 48℃, 50℃, 52℃, 54℃, 55℃, or any two of the aforementioned values. The current density includes, but is not limited to, 2A / dm³. 2 2.5A / dm 2 3A / dm 2 3.5A / dm 2 4.5A / dm 2 Or a range between any two of the foregoing. The electroplating time values ​​include, but are not limited to: 500s, 600s, 700s, 800s, 900s, 1000s, 1100s, 1200s or a range between any two of the foregoing.

[0109] In some embodiments, after the electroplating process is completed, the process further includes cleaning and drying the resulting coating, specifically including the following steps: cleaning the coating with pure water and then drying it at 70℃~120℃.

[0110] The aforementioned composite electroplating solution is used to prepare hydrophobic coatings, simplifying the process steps. The preparation of hydrophobic coatings can be achieved in one step, resulting in high efficiency. Furthermore, the prepared hydrophobic coatings do not contain fluorine-based organic compounds, making them friendly to workers and the environment, thus avoiding environmental pollution. The hydrophobic coatings prepared by the composite electroplating solution of this application show a significantly improved initial water contact angle and significantly improved wear resistance.

[0111] Thirdly, one embodiment of this application provides an electroplated hydrophobic coating.

[0112] An electroplated hydrophobic coating is prepared by the above-described preparation method. The average initial water contact angle (WCA) of the electroplated hydrophobic coating is 110°~113°. After 10,000 wear resistance tests, the average water contact angle (WCA) of the electroplated hydrophobic coating is 105°~106°.

[0113] The water contact angle and wear resistance of the hydrophobic coating prepared by the composite electroplating solution of this application are improved.

[0114] Fourthly, one embodiment of this application provides an electroplating product.

[0115] An electroplating product includes an electroplating substrate and an electroplating hydrophobic coating prepared by the above-described electroplating hydrophobic coating preparation method, wherein the electroplating hydrophobic coating is formed on the surface of the electroplating substrate.

[0116] Example 1

[0117] This embodiment provides an electroplating product.

[0118] The electroplating product of this embodiment includes a pre-plated copper / nickel ABS electroplating substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the ABS electroplating substrate.

[0119] The electroplated product in this embodiment was prepared using the following method.

[0120] A method for preparing an electroplated hydrophobic coating includes the following steps:

[0121] Step 1: Prepare the composite solution.

[0122] Mix hexadecyltrimethylammonium bromide, octadecyltrimethoxysilane, ethanol, pure water, and concentrated sulfuric acid in a mass ratio of 0.125:0.5:100:0.05:0.003, stir rapidly for 30 minutes, and set aside.

[0123] Step 2: Prepare composite nanoparticles.

[0124] 30nm silicon particles were used as nanoparticles and immersed in a piranha solution for 5 seconds to remove impurities from the surface of the nanoparticles and to hydroxylate the surface of the nanoparticles.

[0125] The silica particles were washed once with pure water.

[0126] The silicon particles are dried using freeze-drying equipment to prevent agglomeration, and the silicon particles are then ready for use.

[0127] The temperature of the composite solution was controlled at 30℃, and ultrasonication and stirring were activated. The prepared silicon particles were mixed with the composite solution at a mass ratio of 1:20, and the silicon particles were soaked for 3 hours. After the soaking treatment, the soaking mixture of nanoparticles and composite solution was filtered and then washed three times with ethanol to obtain composite nanoparticles. The composite nanoparticles were baked at 60℃ for 3 hours and then sealed for later use.

[0128] Step 3: Prepare the composite electroplating solution.

[0129] The composite electroplating solution includes components of the following concentrations:

[0130] The conductive salt is 200 g / L, and the conductive salt is potassium sulfate.

[0131] The tank starter is 10g / L, and the tank starter is Anmet brand white bright trivalent chromium tank starter 1687213;

[0132] The wetting agent is 0.5 mL / L, and the wetting agent is Anmet brand white easy bright trivalent chromium wetting agent 1687218;

[0133] The trivalent chromium salt is 18 g / L, and the trivalent chromium salt is chromium sulfate.

[0134] Boric acid 60g / L;

[0135] Composite nanoparticles 1 g / L; and

[0136] The morphology control agent was 20 mg / L, and the morphology control agent was PEG.

[0137] Step 4: Electroplating treatment.

[0138] The pre-plated copper / nickel ABS substrate was electroplated using the composite electroplating solution from step 3. The pH of the composite electroplating solution was controlled at 3, the temperature at 45℃, and the current density at 4.5 A / dm³. 2 The electroplating time is 1200s. An electroplated hydrophobic coating is formed on the surface of the ABS electroplating substrate. The ABS electroplating substrate and the electroplated hydrophobic coating together form an intermediate electroplating product.

[0139] Step 5: After rinsing the intermediate electroplating product, including the ABS electroplating substrate and the electroplated hydrophobic coating, with pure water, dry it with hot air at 70℃ to obtain the electroplated product. The electroplated product includes the electroplated hydrophobic coating. See [link to product details]. Figure 1 As shown, Figure 1 This is an AFM (atomic force microscope) image of the electroplated hydrophobic coating in Example 1.

[0140] The performance of the electroplated product prepared in Example 1 was tested, as shown in Table 1. The average initial water contact angle (WCA) of the hydrophobic coating of the electroplated product was 110°. Figure 2 As shown, Figure 2 The image shows the initial water contact angle (WCA) test result of the electroplated hydrophobic coating in Example 1. Abrasion resistance testing was conducted according to standard GB / T 9266-2009. After 10,000 abrasion cycles, the average water contact angle (WCA) of the electroplated hydrophobic coating was 105°. (See [link to relevant documentation]). Figure 3 As shown, Figure 3 This is a photograph of the water contact angle (WCA) of the electroplated hydrophobic coating in Example 1 after a wear test.

[0141] Example 2

[0142] This embodiment provides an electroplating product.

[0143] The electroplating product of this embodiment includes a metal electroplating substrate and an electroplated hydrophobic coating, wherein the electroplated hydrophobic coating is formed on the surface of the metal electroplating substrate.

[0144] The electroplated product in this embodiment was prepared using the following method.

[0145] A method for preparing an electroplated hydrophobic coating includes the following steps:

[0146] Step 1: Prepare the composite solution.

[0147] The cationic surfactant, silane, ethanol, pure water, and concentrated sulfuric acid were prepared in a mass ratio of 2.5:5:100:0.5:0.03 and stirred rapidly for 30 minutes before use. The cationic surfactant consisted of hexadecyltrimethylammonium bromide and octadecyldimethylbenzylammonium chloride in a 1:1 mass ratio, and the silane consisted of octadecyltrimethoxysilane and hexadecyltrimethoxysilane in a 1:1 mass ratio.

[0148] Step 2: Prepare composite nanoparticles.

[0149] 100nm aluminum oxide particles were used as nanoparticles and immersed in a piranha solution for 20 seconds to remove impurities from the surface of the nanoparticles and to hydroxylate the surface of the nanoparticles.

[0150] The silica particles were washed once with pure water.

[0151] Aluminum oxide granules are dried using freeze-drying equipment to prevent agglomeration. The aluminum oxide granules are then ready for use.

[0152] The temperature of the composite solution was controlled at 55℃, and ultrasonication and stirring were activated. The prepared alumina particles were mixed with the composite solution at a mass ratio of 1:100, and the alumina particles were soaked for 3 hours. After the soaking treatment, the soaking mixture of nanoparticles and composite solution was filtered, and then washed three times with ethanol to obtain composite nanoparticles. The composite nanoparticles were baked at 70℃ for 2 hours and then sealed for later use.

[0153] Step 3: Prepare the composite electroplating solution.

[0154] The composite electroplating solution includes components of the following concentrations:

[0155] The conductive salt is 350 g / L, and the conductive salt is potassium chloride.

[0156] The tank starter is 20g / L, and the tank starter is Anmet brand white bright trivalent chromium tank starter 1687213;

[0157] The wetting agent is 2 mL / L, and the wetting agent is Anmet brand Baiyiliang trivalent chromium wetting agent 1687218;

[0158] 25 g / L of trivalent chromium salt, which is chromium chloride;

[0159] Boric acid 65g / L;

[0160] Composite nanoparticles 10 g / L; and

[0161] The morphology control agent was 500 mg / L, and the morphology control agent was PEG.

[0162] Step 4: Electroplating treatment.

[0163] The metal substrate was electroplated using the composite electroplating solution from step 3, with the pH value of the composite electroplating solution controlled at 4, the temperature at 55℃, and the current density at 2A / dm³. 2 The electroplating time is 500 seconds. A hydrophobic coating is formed on the surface of the metal electroplating substrate, and the metal electroplating substrate and the hydrophobic coating together form an intermediate electroplating product.

[0164] Step 5: After rinsing the intermediate electroplating product with pure water, dry it with hot air at 100℃ to obtain the electroplated product, which includes a hydrophobic coating. See [link to product details]. Figure 4 As shown, Figure 4 The image shown is an AFM image of the electroplated hydrophobic coating from Example 2.

[0165] The performance of the electroplated product prepared in Example 2 was tested, as shown in Table 1. The average initial water contact angle (WCA) of the hydrophobic coating of the electroplated product was 113°. Figure 5 As shown, Figure 5 The image shows the initial water contact angle (WCA) test result of the electroplated hydrophobic coating in Example 2. Abrasion resistance testing was conducted according to standard GB / T 9266-2009. After 10,000 abrasion cycles, the average water contact angle (WCA) of the electroplated hydrophobic coating was 106°. (See [link to relevant documentation]). Figure 6 As shown, Figure 6 This is a photograph of the water contact angle (WCA) of the electroplated hydrophobic coating in Example 1 after a wear test.

[0166] Comparative Example 1

[0167] This comparative example provides an electroplating product.

[0168] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0169] The electroplated hydrophobic coating in this comparative example was formed by conventional electroplating of ordinary trivalent chromium salts, followed by a spraying process to prepare a silane hydrophobic coating on the plating layer.

[0170] The electroplated product in this comparative example was prepared using the following method.

[0171] Step 1: Prepare the electroplating solution.

[0172] The electroplating solution contains components of the following concentrations:

[0173] The conductive salt is 200 g / L, and the conductive salt is potassium sulfate.

[0174] The tank starter is 10g / L, and the tank starter is Anmet brand white bright trivalent chromium tank starter 1687213;

[0175] The wetting agent is 0.5 mL / L, and the wetting agent is Anmet brand white easy bright trivalent chromium wetting agent 1687218;

[0176] The trivalent chromium salt is 18 g / L, and the trivalent chromium salt is chromium sulfate.

[0177] Boric acid 60g / L.

[0178] Step 2: Electroplating treatment.

[0179] The electroplating substrate was electroplated using the electroplating solution from step 1, with the pH value of the solution controlled at 3, the temperature at 45℃, and the current density at 4.5 A / dm³. 2 The electroplating time is 1200s. An electroplated hydrophobic coating is formed on the surface of the electroplating substrate, and the electroplating substrate and the electroplated hydrophobic coating together form an intermediate electroplating product.

[0180] Step 3: After rinsing the intermediate electroplating product with pure water, dry it with hot air at 100℃ to obtain the ordinary trivalent chromium salt electroplated product. Then, use a spraying process to spray commercially available octadecyltrimethoxysilane easy-clean solution onto the trivalent chromium salt electroplated product and bake it at 120℃ for 1 hour to obtain the ordinary electroplated product. See also Figure 7 As shown, Figure 7 AFM image of the electroplated hydrophobic coating for Comparative Example 1.

[0181] The electroplated product prepared in Comparative Example 1 was subjected to performance tests, as shown in Table 1. The average initial water contact angle (WCA) of the hydrophobic coating of the electroplated product was 106°. Figure 8 As shown, Figure 8 The image shows the initial water contact angle (WCA) test result of the electroplated hydrophobic coating in Comparative Example 1. Abrasion resistance testing was conducted according to standard GB / T 9266-2009. After 10,000 abrasion cycles, the average water contact angle (WCA) of the electroplated hydrophobic coating was 93°. (See [reference needed]). Figure 9 As shown, Figure 9 This is a photograph of the water contact angle (WCA) of the electroplated hydrophobic coating in Comparative Example 1 after wear testing.

[0182] Comparative Example 2

[0183] This comparative example provides an electroplating product.

[0184] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0185] The preparation method of the electroplated product in this comparative example is basically the same as that in Example 1. The difference is that no morphology control agent is added to the composite electroplating solution formulation in this comparative example 2.

[0186] See Figure 10 As shown, Figure 10 The image shown is an AFM image of the electroplated hydrophobic coating in Comparative Example 2. The prepared electroplated products were tested, as shown in Table 1. The average initial water contact angle (WCA) of the electroplated hydrophobic coating was 100°. Figure 11 As shown, Figure 11 The image shown is a photograph of the initial water contact angle (WCA) test of the electroplated hydrophobic coating in Comparative Example 2. Abrasion resistance testing was conducted according to standard GB / T 9266-2009. After 10,000 abrasion cycles, the average water contact angle (WCA) of the electroplated hydrophobic coating was 84°. (See [reference needed]). Figure 12 As shown, Figure 12 This is a photograph of the water contact angle (WCA) of the electroplated hydrophobic coating after wear testing, as shown in Comparative Example 2.

[0187] Comparative Example 3

[0188] This comparative example provides an electroplating product.

[0189] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0190] The preparation method of the electroplating product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 3, no composite nanoparticles are added to the composite electroplating solution formulation.

[0191] The prepared electroplated products were tested, as shown in Table 1.

[0192] Comparative Example 4

[0193] This comparative example provides an electroplating product.

[0194] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0195] The preparation method of the electroplating product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 4, the concentration of composite nanoparticles in the composite electroplating solution formula is 0.5 g / L.

[0196] The prepared electroplated products were tested, as shown in Table 1.

[0197] Comparative Example 5

[0198] This comparative example provides an electroplating product.

[0199] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0200] The preparation method of the electroplating product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 5, the concentration of composite nanoparticles in the composite electroplating solution formula is 15 g / L.

[0201] The prepared electroplated products were tested, as shown in Table 1.

[0202] Comparative Example 6

[0203] This comparative example provides an electroplating product.

[0204] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0205] The preparation method of the electroplating product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 6, the mass ratio of hexadecyltrimethylammonium bromide, octadecyltrimethoxysilane, ethanol, pure water and concentrated sulfuric acid in the composite solution is 0.05:0.5:100:0.05:0.003, that is, the mass ratio of cationic surfactant to silane is less than 0.25.

[0206] The prepared electroplated products were tested, as shown in Table 1.

[0207] Comparative Example 7

[0208] This comparative example provides an electroplating product.

[0209] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0210] The preparation method of the electroplating product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 7, the mass ratio of hexadecyltrimethylammonium bromide, octadecyltrimethoxysilane, ethanol, pure water and concentrated sulfuric acid in the composite solution is 0.5:0.5:100:0.05:0.003, that is, the mass ratio of cationic surfactant to silane is 1, which is much greater than 0.5.

[0211] The prepared electroplated products were tested, as shown in Table 1.

[0212] Comparative Example 8

[0213] This comparative example provides an electroplating product.

[0214] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0215] The preparation method of the electroplated product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 8, the concentration of morphology control agent in the composite electroplating solution formula is 10 mg / L.

[0216] The prepared electroplated products were tested, as shown in Table 1.

[0217] Comparative Example 9

[0218] This comparative example provides an electroplating product.

[0219] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0220] The preparation method of the electroplated product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 9, the concentration of the morphology control agent in the composite electroplating solution formula is 600 mg / L.

[0221] The prepared electroplated products were tested, as shown in Table 1.

[0222] Comparative Example 10

[0223] This comparative example provides an electroplating product.

[0224] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0225] The preparation method of the electroplated product in this comparative example is basically the same as that in Example 1, except that the concentration of the morphology control agent in the composite electroplating solution formula in this comparative example 10 is 1000 mg / L.

[0226] The prepared electroplated products were tested, as shown in Table 1.

[0227] Comparative Example 11

[0228] This comparative example provides an electroplating product.

[0229] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0230] The preparation method of the electroplated product in this comparative example is basically the same as that in Example 1. The difference is that in step 2 of this comparative example 11, when preparing composite nanoparticles, the nanoparticles and composite solution are in a mass ratio of 1:10.

[0231] The prepared electroplated products were tested, as shown in Table 1.

[0232] Comparative Example 12

[0233] This comparative example provides an electroplating product.

[0234] The electroplated product in this comparative example includes an electroplated substrate and an electroplated hydrophobic coating, the electroplated hydrophobic coating being formed on the surface of the electroplated substrate.

[0235] The preparation method of the electroplated product in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example 12, in step 2, when preparing composite nanoparticles, the nanoparticles and composite solution are in a mass ratio of 1:120.

[0236] The prepared electroplated products were tested, as shown in Table 1.

[0237] Table 1

[0238]

[0239] Comparative Example 1 does not contain composite nanoparticles or morphology control agents. The electroplated hydrophobic coating of Comparative Example 1 is formed by conventional electroplating of ordinary trivalent chromium salts, followed by a spraying process to prepare a silane hydrophobic coating on the coating. The coating preparation process of the spraying process has more steps than that of Example 1 and Example 2. In comparison, the process of Comparative Example 1 is more complicated, the process steps are more cumbersome, and the cost is significantly increased, making it unsuitable for mass production.

[0240] Table 1 shows that the electroplated hydrophobic coatings of the electroplated products prepared in Examples 1 and 2 of this application can be achieved using a one-step process. The average initial water contact angle (WCA) of the electroplated hydrophobic coating prepared by the composite electroplating solution in Example 1 is 110°. See the test photograph of the initial water contact angle (WCA) of the electroplated hydrophobic coating prepared in Example 1. Figure 2 As shown, the average initial water contact angle (WCA) of the electroplated hydrophobic coating prepared by the composite electroplating solution in Example 2 is 113°. See the test photograph of the initial water contact angle (WCA) of the electroplated hydrophobic coating prepared in Example 2. Figure 5 As shown, in Comparative Example 2, the composite electroplating solution without morphology control agent resulted in an average initial water contact angle (WCA) of only 100° for the electroplated hydrophobic coating. See the test photograph of the initial water contact angle (WCA) of the electroplated hydrophobic coating in Comparative Example 1. Figure 10 As shown, the composite electroplating solution using morphology control agents in this application significantly improves the initial water contact angle of the electroplated hydrophobic coating.

[0241] Furthermore, in Example 1, the water contact angle of the electroplated hydrophobic coating after 10,000 wear cycles was 105°. See the WCA test photograph of the water contact angle of the electroplated hydrophobic coating prepared in Example 1 after the wear test. Figure 3 As shown, the water contact angle (WCA) of the electroplated hydrophobic coating without morphology control agent in Comparative Example 2 after 10,000 wear cycles is 84°. See the WCA test photograph of the electroplated hydrophobic coating prepared in Comparative Example 2 after wear testing. Figure 12 As shown, the composite electroplating solution containing a morphology control agent in this application can improve the initial water contact angle and wear resistance of the electroplated hydrophobic coating.

[0242] AFM (Atomic Force Microscopy) image of the electroplated hydrophobic coating prepared in Example 1 is shown below. Figure 1 As shown, the AFM image of the electroplated hydrophobic coating prepared in Example 2 is available in [reference needed]. Figure 4 As shown, the AFM image of the composite electroplating solution without morphology control agent in Comparative Example 2 is shown below. Figure 10 As shown, by Figure 10 and Figure 1 , Figure 4The comparison shows that, in Comparative Example 2 Figure 10 The number of micro / nano morphologies in the electroplated hydrophobic coating decreased significantly. See also Figure 1 and Figure 4 As can be seen from the comparison of atomic force microscopy images, the electroplated hydrophobic coating prepared in this invention has a specific microstructure. The synergistic effect of this microstructure and the silane hydrophobic material further enhances the hydrophobic properties of the electroplated hydrophobic coating. (Comparison) Figure 2 and Figure 3 , Figure 5 and Figure 6 As observed by atomic force microscopy, the electroplated hydrophobic coating with microscopic morphology does not wear down to the pits during abrasion, thus preserving more of the hydrophobic material within the pits. In contrast, the hydrophobic material at the points of direct contact with the friction medium is damaged or detached, resulting in decreased hydrophobicity. Compared to electroplated hydrophobic coatings without microscopic morphology, its wear resistance is poor. Therefore, the electroplated hydrophobic coating prepared by the composite electroplating solution of this application exhibits an increased water contact angle and improved wear resistance.

[0243] Comparing Comparative Examples 3-5 with Example 1, it can be seen that the composite electroplating solution formulation in Comparative Example 3 did not contain composite nanoparticles, while the composite nanoparticle concentration in the composite electroplating solution formulation in Comparative Example 4 was 0.5 g / L. The lack of composite nanoparticles or their insufficient content resulted in poor hydrophobicity. The absence of composite nanoparticles, i.e., the lack of hydrophobic material, caused the coating surface to only have micro-nano structures, making it hydrophilic (WCA 34°). Furthermore, after friction, the micro-nano structures were slightly damaged, further worsening the hydrophilicity and increasing the WCA (WCA 43°). However, when there is too little hydrophobic material, there is insufficient hydrophobic material adhering to the coating surface, and the chromium coating still directly contacts the water (the contact angle between ordinary electroplated chromium and water is 75°). Therefore, it cannot achieve the 110° or higher required for normal hydrophobic material coverage. In Comparative Example 5, the concentration of composite nanoparticles in the composite electroplating solution formulation was 15 g / L. The excessive content of composite nanoparticles resulted in poor wear resistance. Due to the large number of particles, the coating became loose during electroplating, making it easier for the coating to peel off during the friction test, resulting in a significant decrease in WCA after the scrubbing resistance test.

[0244] Comparing Comparative Examples 6 and 7 with Example 1, it can be seen that in Comparative Example 6, the ratio of cationic surfactant mass to silane mass is less than 0.25, indicating a low cationic surfactant content, resulting in poor hydrophobic properties. This is because the cationic surfactant attached to the nanoparticles can improve the efficiency of composite nanoparticle embedding in the coating under an electric field. However, when there is too little cationic surfactant on the nanoparticles, the number of composite nanoparticles embedded in the coating is too small, resulting in insufficient hydrophobic material in the coating and thus poor hydrophobic properties. In Comparative Example 7, the ratio of cationic surfactant mass to silane mass is greater than 0.5, indicating an excessively high cationic surfactant content, which also leads to poor hydrophobic properties. This is because there is too little hydrophobic material in the composite nanoparticles, resulting in insufficient hydrophobic material in the coating and inability to exert its hydrophobic properties.

[0245] Comparing Comparative Examples 8-10 with Example 1, it can be seen that in Comparative Example 8, the concentration of the morphology control agent in the composite electroplating solution formulation was 10 mg / L. This concentration was too low, resulting in the lack of growth of micro / nano morphologies in the coating, leaving only hydrophobic materials and failing to achieve the desired effect of combining micro / nano morphologies with hydrophobic materials to obtain better hydrophobic properties. In Comparative Example 9, the concentration of the morphology control agent in the composite electroplating solution formulation was 600 mg / L, and in Comparative Example 10, the concentration was 1000 mg / L. These excessively high concentrations restricted the growth of micro / nano morphologies and resulted in uneven coating. Too much morphology control agent formed excessively large and numerous non-conductive areas on the coating surface, significantly reducing the number of micro / nano morphologies and causing uneven coating surface, thus failing to achieve the desired effect of combining micro / nano morphologies with hydrophobic materials.

[0246] Comparing Comparative Examples 11 and 12 with Example 1, it can be seen that in Comparative Example 11, in step 2, when preparing the composite nanoparticles, the mass ratio of nanoparticles to the composite solution is 1:10. The excessive nanoparticle content results in some nanoparticles not being bonded to the cationic surfactant and silane, or each nanoparticle not being completely covered by the cationic surfactant and silane. When using the composite nanoparticles, some of them are ineffective or contain too little hydrophobic material, ultimately leading to poor hydrophobicity of the electroplated layer. In Comparative Example 12, in step 2, when preparing the composite nanoparticles, the mass ratio of nanoparticles to the composite solution is 1:120. The insufficient nanoparticle content results in low production efficiency of the composite nanoparticles, increasing production costs.

[0247] In summary, the composite electroplating solution of this application can be used to prepare hydrophobic coatings, simplifying the process steps. It allows for one-step preparation of hydrophobic coatings with high efficiency. Furthermore, the prepared hydrophobic coating does not contain fluorine-based organic compounds, making it environmentally friendly and avoiding pollution. The average initial water contact angle (WCA) of the hydrophobic coating prepared with the composite electroplating solution of this application is 110°~113°, and after 10,000 wear resistance tests, the average water contact angle (WCA) of the hydrophobic coating is 105°~106°. Compared to traditional technologies, the composite electroplating solution of this application can improve both the water contact angle and wear resistance of the prepared hydrophobic coating.

[0248] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0249] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0250] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A composite electroplating solution, characterized in that, include: Solvent; Conductive salt concentration: 200g / L~350g / L; Starter agent: 10g / L~20g / L; Wetting agent: 0.5 mL / L ~ 2 mL / L; Trivalent chromium salts: 18g / L~25g / L; Boric acid 60g / L~65g / L; Composite nanoparticles 1g / L~10g / L; and Morphology control agent: 20 mg / L ~ 500 mg / L; The composite nanoparticles are formed by immersing nanoparticles in a composite solution. The nanoparticles include one or more of silicon particles, silica particles, titanium dioxide particles, and aluminum oxide particles. The composite solution includes the following components: cationic surfactant, silane, ethanol, water, and acid. The mass ratio of cationic surfactant, silane, ethanol, water, and acid is (0.125~2.5):(0.5~5):100:(0.05~0.5):(0.003~0.03), and 1 / 4 ≤ mass of cationic surfactant / mass of silane ≤ 1 / 2.

2. The composite electroplating solution according to claim 1, characterized in that, The composite electroplating solution also meets at least one of the following conditions: (1) The conductive salt includes one or more of sodium chloride, potassium chloride, ammonium chloride, potassium sulfate, and ammonium sulfate; (2) The trivalent chromium salts include one or more of chromium sulfate, chromium chloride, and chromium formate.

3. The composite electroplating solution according to claim 1, characterized in that, The morphology control agent includes one or both of PEG and Janus Green.

4. The composite electroplating solution according to claim 1, characterized in that, The nanoparticles have a particle size of 30nm to 200nm.

5. The composite electroplating solution according to any one of claims 1 to 4, characterized in that, The composite electroplating solution also meets at least one of the following conditions: (1) The cationic surfactant includes one or more of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and octadecyldimethylbenzylammonium chloride; (2) The silane includes one or more of octadecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane; (3) The acid includes one or more of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid.

6. A method for preparing composite nanoparticles according to any one of claims 1 to 5, characterized in that, Includes the following steps: After pretreatment, cleaning and filtration, and freeze-drying, the nanoparticles are immersed in a composite solution to form an immersion mixture. The immersion mixture is then filtered and dried to obtain the composite nanoparticles.

7. The preparation method according to claim 6, characterized in that, The preparation method satisfies at least one of the following conditions: (1) The pretreatment includes the following steps: immersing the nanoparticles in a piranha solution for 5s to 20s to remove impurities from the surface of the nanoparticles and to hydroxylate the surface of the nanoparticles; (2) The cleaning and filtration process includes the following steps: cleaning and filtering the nanoparticles with pure water at least once; (3) Immersion in the composite solution specifically includes the following steps: after mixing the nanoparticles with the composite solution, immerse the nanoparticles in the solution for 10 min to 3 h under ultrasonic and stirring conditions; wherein the mass ratio of the nanoparticles to the composite solution is 1:(20~100), and the temperature of the composite solution is controlled at 30℃~55℃; (4) The soaking mixture is filtered and then dried, including the following steps: the soaking mixture is filtered and then rinsed with ethanol at least three times; the collected solid particles are baked at 60℃~70℃ for 2h~3h to obtain the composite nanoparticles.

8. A method for preparing an electroplated hydrophobic coating, characterized in that, Includes the following steps: The composite electroplating solution according to any one of claims 1 to 5 is used to electroplat the substrate to be electroplated, thereby forming an electroplated hydrophobic coating on the surface of the substrate.

9. The method for preparing an electroplated hydrophobic coating according to claim 8, characterized in that, During electroplating, at least one of the following parameters must be met: the pH value of the composite electroplating solution is controlled to be 3-4, the temperature is controlled to be 45℃-55℃, and the current density is controlled to be 2A / dm³. 2 ~4.5A / dm 2 The electroplating time is 500s~1200s.

10. The method for preparing an electroplated hydrophobic coating according to any one of claims 8 to 9, characterized in that, After the electroplating process is completed, the process also includes cleaning and drying the resulting coating, specifically including the following steps: After cleaning the coating with pure water, it is dried at 70℃~120℃.

11. An electroplated hydrophobic coating, characterized in that, The electroplated hydrophobic coating is prepared by any one of claims 8 to 10, wherein the average initial water contact angle (WCA) of the electroplated hydrophobic coating is 110° to 113°, and after 10,000 wear resistance tests, the average water contact angle (WCA) of the electroplated hydrophobic coating is 105° to 106°.

12. An electroplating product, characterized in that, The invention includes an electroplated substrate and an electroplated hydrophobic coating prepared by the preparation method according to any one of claims 8 to 10, wherein the electroplated hydrophobic coating is formed on the surface of the electroplated substrate.

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