Treatment method of electroplating liquid and testing method of dispersing agent in sample to be tested

Abstract

The invention discloses an electroplating liquid treatment method and a method for testing a dispersing agent in a to-be-tested sample, and relates to the technical field of analysis and testing. The treatment method of the electroplating liquid comprises the following steps that a buffer solution and the electroplating liquid are provided, and the electroplating liquid comprises a dispersing agent and graphene; and mixing the buffer solution and the electroplating solution, carrying out first filtration, and removing the precipitate to obtain the sample to be detected. According to the treatment method of the electroplating solution, the buffer solution is added into the electroplating solution, the buffer solution enables a system to have a stable pH value, the stability of the system is improved, and the buffer solution can change the Zeta potential value of the surfaces of graphene particles, so that a dispersing agent connected with the graphene particles falls off from the surfaces of the graphene; therefore, the dispersing agent cannot be taken away when graphene is subsequently filtered, and the accuracy of liquid chromatography detection of the dispersing agent is improved.

Description

Technical Field

[0001] The present application relates to the technical field of testing and analysis, and in particular to a method for processing an electroplating solution and a method for testing a dispersant in a sample to be tested. Background Art

[0002] Graphene is a sp 2 Two-dimensional nanomaterials with hybrid-connected single carbon atomic layers have excellent properties such as high conductivity, high thermal conductivity, high strength, high flexibility, strong chemical inertness, and excellent gas barrier properties. They show great application potential in electrical conductivity, thermal conductivity, anti-static, anti-corrosion coatings, and metal current collector materials.

[0003] Due to the strong π-π bond between graphene sheet particles, agglomeration easily occurs, resulting in poor uniform dispersion of graphene in the solution system, which seriously affects the application of graphene in coatings and plating. In order to improve the uniform dispersion of graphene in liquid phase solutions, a dispersant is usually introduced to disperse the graphene particles so that they can be evenly dispersed to achieve the smooth progress of the electrodeposition process. The dispersant molecules ionize the hydrophilic end and the graphene-philic end in the aqueous solution, and the graphene-philic end is connected to the graphene particles and then coated on the periphery of the graphene particles. Due to the electrostatic repulsion of the dispersant molecules, the graphene particles are dispersed.

[0004] In metal graphene electroplating solutions, liquid chromatography is usually used to control the concentration of dispersants. Since dispersants exist in the metal graphene electroplating solution in the form of molecules and ion fragments, the metal graphene electroplating solution needs to be filtered before liquid chromatography testing. The dispersant ions connected to the graphene particles are directly filtered out, affecting the actual concentration of the dispersant in the metal graphene electroplating solution. Summary of the invention

[0005] In view of this, the present application provides a method for treating an electroplating solution and a method for testing a dispersant in a sample to be tested.

[0006] The embodiment of the present application is implemented as follows. In a first aspect, the embodiment of the present application provides a method for treating an electroplating solution, comprising the following steps:

[0007] Providing a buffer solution and an electroplating solution, wherein the electroplating solution includes a dispersant and graphene;

[0008] The buffer solution is mixed with the electroplating solution, and the precipitate is removed after a first filtration to obtain a sample to be tested. Optionally, in some embodiments of the present application, the buffer solution is an acidic buffer solution; and / or

[0009] The buffer comprises one or more of a phosphate buffer and an acetic acid-sodium acetate buffer.

[0010] Optionally, in some embodiments of the present application, the pH of the acidic buffer is 3.6 to 6; and / or

[0011] The phosphate buffer is prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate; and / or

[0012] The acetic acid-sodium acetate buffer is prepared from acetic acid and sodium acetate. In the acetic acid-sodium acetate buffer, the mass concentration of the sodium acetate is 5.1 g / L to 109.2 g / L, and the volume concentration of the acetic acid is 2.28 mL / L to 70 mL / L.

[0013] Optionally, in some embodiments of the present application, the dispersant includes one or more of sulfonates, sulfates, and polyethers; wherein the sulfonates include one or more of sodium polynaphthalene sulfonate and sodium dodecylbenzene sulfonate; the sulfates include sodium dodecyl sulfate; the polyethers include alkylphenol polyoxyethylene ether; and / or

[0014] The volume ratio of the buffer solution to the electroplating solution is (70-200):10; and / or

[0015] In the electroplating solution, at least part of the dispersant is connected to the graphene; and / or

[0016] The sample to be tested includes the dispersant.

[0017] Optionally, in some embodiments of the present application, in the electroplating solution, the mass concentration of the graphene is 0.8 g / L; and / or

[0018] The electroplating solution further comprises a metal salt, wherein the metal salt comprises a nickel salt; and / or

[0019] The electroplating solution also includes a solvent.

[0020] Optionally, in some embodiments of the present application, the nickel salt includes one or more of nickel sulfamate and nickel chloride; wherein the mass concentration of the nickel sulfamate is 300 g / L to 400 g / L; the mass concentration of the nickel chloride is 25 g / L to 40 g / L; and / or

[0021] The solvent is selected from one or more of water, ethanol, isopropanol, N-methylpyrrolidone, dichloromethane, xylene, dichlorobenzene, ethylene glycol and toluene.

[0022] Optionally, in some embodiments of the present application, after mixing the buffer solution and the electroplating solution, stirring is further included, and the stirring time is 20 min to 50 min; and / or

[0023] The first filtering method includes microporous membrane filtration.

[0024] In a second aspect, the present application also provides a method for testing a dispersant in a sample to be tested, comprising the following steps:

[0025] Providing a sample to be tested after being treated by any of the above-mentioned electroplating solution treatment methods;

[0026] The sample to be tested is subjected to a liquid chromatography test to obtain the concentration of the dispersant.

[0027] Optionally, in some embodiments of the present application, the liquid chromatography test on the sample to be tested includes: after the sample to be tested is subjected to a second filtration, adding the sample to be tested to a chromatography bottle for liquid chromatography test; wherein the second filtration method is needle filter filtration.

[0028] Optionally, in some embodiments of the present application, the mobile phase of the liquid chromatography test comprises a mixture of methanol and an aqueous solution of glacial acetic acid; wherein the volume ratio of the methanol to the aqueous solution of glacial acetic acid is (10-40): (60-90); and / or

[0029] The flow rate of the mobile phase of the liquid chromatography test is 0.8 mL / min to 1.5 mL / min; and / or

[0030] The wavelength of the ultraviolet detector of the liquid chromatography test is 268nm to 288nm; and / or

[0031] The temperature of the column oven of the liquid chromatography test is 28°C to 35°C; and / or

[0032] The elution time of the liquid chromatography test is 24 min to 45 min.

[0033] The present application provides a method for treating an electroplating solution, wherein a buffer solution is added to the electroplating solution. The buffer solution allows the system to have a stable pH value, thereby improving the stability of the system. The buffer solution can also change the Zeta potential value of the surface of graphene particles, causing the dispersant connected to the graphene particles to fall off the graphene surface, thereby preventing the dispersant from being taken away when the graphene is subsequently filtered, thereby improving the accuracy of liquid chromatography detection of the dispersant. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0035] Figure 1 is a flow chart of a method for treating an electroplating solution provided in an embodiment of the present application;

[0036] Figure 2 It is a flow chart of a method for testing a dispersant in a sample to be tested provided in an embodiment of the present application. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0038] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0039] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0040] In the present application, "at least one" means one or more, and "plurality" means two or more. "One or several", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0041] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0042] The technical solution of this application is as follows:

[0043] First, see Figure 1 The present invention provides a method for treating an electroplating solution, comprising the following steps:

[0044] S11, providing a buffer solution and an electroplating solution, wherein the electroplating solution includes a dispersant and graphene;

[0045] S12, mixing the buffer solution and the electroplating solution, performing a first filtration and removing the precipitate to obtain a sample to be tested.

[0046] It should be noted that a buffer solution refers to a solution that has the ability to maintain a relatively stable pH. The buffer solution can offset and reduce the effect of an external strong acid or base on the pH of the solution to a certain extent, thereby maintaining the pH value of the solution within a certain range without significant changes due to dilution or the addition of a small amount of acid or base. The buffer solution has different pH values ​​and buffer capacities depending on the conjugate acid-base pair and the amount of its substance.

[0047] The present application provides a method for treating an electroplating solution, wherein a buffer solution is added to the electroplating solution. The buffer solution allows the system to have a stable pH value, thereby improving the stability of the system. The buffer solution can also change the Zeta potential value of the surface of graphene particles, causing the dispersant connected to the graphene particles to fall off the graphene surface, thereby preventing the dispersant from being taken away when the graphene is subsequently filtered, thereby improving the accuracy of liquid chromatography detection of the dispersant.

[0048] Specifically, the buffer solution can provide a solution environment with a stable pH. For acidic or alkaline solutions, that is, there are too many hydrogen ions or hydroxide ions. According to the principle that like charges attract and unlike charges repel, too many hydrogen ions or hydroxide ions will change the charge distribution on the surface of the graphene particles, that is, change the Zeta potential on the surface of the graphene particles. The closer the pH of the solution is to 7, the smaller the absolute value of the Zeta potential is, and the easier it is for graphene to agglomerate. Under the action of electrostatic attraction, the agglomeration of graphene can promote the desorption of the dispersant from the graphene surface.

[0049] In some embodiments, the buffer is an acidic buffer. Further, the pH of the acidic buffer is 3.6 to 6, for example, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8 or a range between any two values. Within the pH range, when performing a liquid chromatography test, the mobile phase is acidic, and the acidic buffer can ensure the stability of the test conditions.

[0050] In some embodiments, the buffer comprises one or more of a phosphate buffer and an acetic acid-sodium acetate buffer.

[0051] It should be noted that the buffer can be obtained by preparing raw materials to a suitable pH. For example, the phosphate buffer can be prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate. Specifically, the preparation method of the phosphate buffer is as follows:

[0052] S111, prepare 0.2 mol / L NaH2PO4 solution and 0.2 mol / L Na2HPO4 solution;

[0053] S112. Prepare the 0.2 mol / L NaH2PO4 solution and the 0.2 mol / L Na2HPO4 solution according to Table 1 to obtain a phosphate buffer solution of a desired pH.

[0054] Table 1

[0055]

[0056] It should be noted that Table 1 is configured based on 100 mL of phosphate buffer. In actual operation, different total volumes of phosphate buffer can be configured according to needs.

[0057] In some embodiments, the preparation method of the 0.2 mol / L NaH2PO4 solution includes: weighing 31.2 g Na2HPO4·12H2O or 27.6 g NaH2PO4·H2O, and adding distilled water to 1000 mL to dissolve.

[0058] In some embodiments, the preparation method of the 0.2 mol / L Na2HPO4 solution includes: weighing 71.632 g Na2HPO4·12H2O, or 53.6 g Na2HPO4·7H2O, or 35.6 g Na2HPO4·2H2O, and adding distilled water to 1000 mL to dissolve.

[0059] The acetic acid-sodium acetate buffer can be prepared from acetic acid and sodium acetate. Specifically, the preparation method of the acetic acid-sodium acetate buffer is as follows:

[0060] S113, prepare 0.2 mol / L CH3COOH solution and 0.2 mol / L CH3COONa solution;

[0061] S114. The 0.2 mol / L CH3COOH solution and the 0.2 mol / L CH3COONa solution are configured according to Table 2 to obtain an acetic acid-sodium acetate buffer solution of a desired pH.

[0062] Table 2

[0063]

[0064]

[0065] It should be noted that Table 2 is configured based on 20 mL of acetic acid-sodium acetate buffer. In actual operation, acetic acid-sodium acetate buffer of different total volumes can be configured according to needs.

[0066] In some embodiments, the preparation method of the 0.2 mol / L CH3COOH solution includes: weighing 33.3 mL of 36% CH3COOH, and adding distilled water to dissolve it in 1000 mL.

[0067] In some embodiments, the preparation method of the 0.2 mol / L CH3COONa solution includes: weighing 16.4 g CH3COONa, adding distilled water to 1000 mL to dissolve it.

[0068] In some embodiments, in the acetic acid-sodium acetate buffer, the mass concentration of sodium acetate is 5.1 g / L to 109.2 g / L, and the volume concentration of acetic acid is 2.28 mL / L to 70 mL / L. It is understood that the mass concentration of sodium acetate and the volume concentration of acetic acid can be adjusted according to actual needs to obtain an acetic acid-sodium acetate buffer of a desired pH.

[0069] In some embodiments, the dispersant includes one or more of sulfonates, sulfates, and polyethers.

[0070] Specifically, the sulfonates include one or more of sodium polynaphthalene sulfonate and sodium dodecylbenzene sulfonate.

[0071] The sulfates include sodium lauryl sulfate.

[0072] The polyethers include alkylphenol polyoxyethylene ethers.

[0073] In some embodiments, in the electroplating solution, the mass concentration of the graphene is 0.5 g / L to 1.5 g / L, for example, 0.6 g / L, 0.8 g / L, 1 g / L, 1.2 g / L or a range between any two values.

[0074] In some embodiments, in the electroplating solution, at least a portion of the dispersant is connected to the graphene. Specifically, at least a portion of the dispersant and the graphene interact with each other through electrostatic attraction.

[0075] In some embodiments, the electroplating solution further includes a metal salt.

[0076] Furthermore, the metal salt includes nickel salt.

[0077] In some embodiments, the nickel salt includes one or more of nickel sulfamate and nickel chloride.

[0078] Furthermore, the mass concentration of the nickel sulfamate is 300 g / L to 400 g / L, for example, 310 g / L, 320 g / L, 330 g / L, 340 g / L, 350 g / L, 360 g / L, 370 g / L, 380 g / L, 390 g / L or a range between any two values.

[0079] The mass concentration of the nickel chloride is 25 g / L to 40 g / L, for example, 28 g / L, 30 g / L, 32 g / L, 35 g / L, 38 g / L or a range between any two values.

[0080] It can be understood that the electroplating solution can be used for electroplating metal coatings.

[0081] In some embodiments, the electroplating solution further comprises a solvent. Further, the solvent is selected from one or more of water, ethanol, isopropanol, N-methylpyrrolidone (NMP), dichloromethane, xylene, dichlorobenzene, ethylene glycol, and toluene.

[0082] In some embodiments, the volume ratio of the buffer solution to the electroplating solution is (70-200):10, for example, 80:10, 90:10, 100:10, 120:10, 150:10, 180:10 or any range between two values. Within the volume ratio range, the buffer solution is beneficial to change the Zeta potential value of the graphene particle surface, so that the dispersant connected to the graphene particles falls off the graphene surface.

[0083] In some embodiments, the mixing of the buffer solution and the electroplating solution further includes stirring. Furthermore, the stirring time is 20 min to 50 min, for example, 22 min, 25 min, 28 min, 30 min, 32 min, 35 min, 38 min or a range between any two values. Within the time range, it is beneficial to fully mix the buffer solution and the electroplating solution, so that the dispersant connected to the graphene falls off, and the dispersant is prevented from being taken away by the graphene when the graphene is removed.

[0084] In some embodiments, the first filtering method comprises microporous membrane filtration.

[0085] It should be noted that the pore size of the microporous filter membrane can be selected according to the particle size of the graphene in the electroplating solution and the accuracy of the existing detection device, so as to remove the graphene in the electroplating solution and other solid particles with larger particle sizes in the electroplating solution as much as possible, improve the accuracy of dispersant detection, and avoid the presence of graphene or other solid particles with larger particle sizes affecting the concentration of the dispersant.

[0086] In some embodiments, the sample to be tested includes the dispersant.

[0087] Second, see Figure 2 The present application also provides a method for testing a dispersant in a sample to be tested, comprising the following steps:

[0088] S21: providing a sample to be tested after being treated by the above-mentioned electroplating solution treatment method;

[0089] S22: Performing a liquid chromatography test on the sample to be tested to obtain the concentration of the dispersant.

[0090] The liquid chromatography is a method for achieving separation by causing the target substance in the test solution to undergo specific adsorption and desorption on the chromatographic column through different compositions and ratios of mobile phases, and then being detected and converted on a detector to form a chromatogram for quantitative analysis.

[0091] In some embodiments, the performing liquid chromatography test on the sample to be tested includes: performing a second filtration on the sample to be tested and then adding the sample to a chromatography bottle for liquid chromatography test.

[0092] In some embodiments, the second filtering method is a needle filter filtration. The needle filter can further filter out possible insoluble particles to protect the chromatographic column and improve the utilization rate of the liquid chromatograph.

[0093] In some embodiments, the mobile phase of the liquid chromatography test includes a mixture of methanol and glacial acetic acid aqueous solution. It should be noted that the glacial acetic acid aqueous solution is a solution formed by dissolving glacial acetic acid in water, wherein the concentration of glacial acetic acid can be 0.2 vol%, wherein vol% represents volume fraction.

[0094] Furthermore, in the mixed liquid, the volume ratio of the methanol to the glacial acetic acid aqueous solution is (10-40):(60-90), for example, it can be 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60 or a range between any two ratios.

[0095] In some embodiments, the flow rate of the mobile phase of the liquid chromatography test is 0.8 mL / min to 1.5 mL / min, for example, it can be 0.8 mL / min, 0.9 mL / min, 1 mL / min, 1.1 mL / min, 1.2 mL / min, 1.3 mL / min, 1.4 mL / min, 1.5 mL / min or a range between any two values.

[0096] In some embodiments, the wavelength of the ultraviolet detector of the liquid chromatography test is 268nm~288nm, for example, it can be 269nm, 270nm, 271nm, 272nm, 273nm, 274nm, 275nm, 276nm, 277nm, 278nm, 279nm, 280nm, 281nm, 282nm, 283nm, 284nm, 285nm, 286nm, 287nm or a range between any two values.

[0097] In some embodiments, the temperature of the column oven of the liquid chromatography test is 28°C to 35°C, for example, it can be 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C or a range between any two values.

[0098] In some embodiments, the elution time of the liquid chromatography test is 24 min to 45 min, for example, it can be 25 min, 30 min, 35 min, 40 min or a range between any two values.

[0099] In this way, under the above-mentioned liquid chromatography test conditions, it is conducive to efficiently and accurately testing the concentration of the dispersant.

[0100] In some embodiments, the liquid chromatography test is high performance liquid chromatography. When using high performance liquid chromatography, the sample to be tested is injected into the chromatographic column and moves in the stationary phase by pressure. Due to the different interactions between different substances of the tested species and the stationary phase, different substances leave the chromatographic column in sequence, and different peak signals are obtained through the detector. Finally, the substances contained in the tested object are determined by analyzing and comparing these signals.

[0101] It should be noted that after the liquid chromatography test, a chromatogram can be obtained, and the concentration of the dispersant can be obtained by integrating the chromatogram. The concentration of the dispersant is the volume concentration of the dispersant.

[0102] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and are not limitations of the present application.

[0103] Example 1

[0104] This embodiment provides a method for treating an electroplating solution, comprising:

[0105] Buffer solution preparation: weigh 20.4 g of anhydrous sodium acetate and 70 mL of glacial acetic acid solution, dilute to 1000 mL with water to obtain a buffer solution with a pH of 3.6;

[0106] Metal graphene electroplating solution: including dispersant sodium polynaphthalenesulfonate with a volume concentration of 20 mL / L, graphene with a mass concentration of 0.8 g / L, and nickel sulfamate with a mass concentration of 300 g / L;

[0107] Mixing reaction: In a fume hood, take 10 mL of metal graphene electroplating solution, slowly add the prepared buffer solution to 100 mL, and stir for 30 min;

[0108] Preparation of samples to be tested: The particle size distribution of graphene particles in the metal graphene electroplating solution is: D03 = 0.052 μm, D10 = 0.063 μm, D25 = 0.081 μm, D50 = 0.489 μm, D97 = 2.267 μm. Since the minimum pore size of the existing microporous filter membrane is 0.05 μm, a microporous filter membrane with a pore size of 0.05 μm is selected. The solution after the above mixed reaction is added to the filter cup for suction filtration to remove the water-insoluble solid particles therein, and the filtrate is the sample to be tested.

[0109] Accordingly, this embodiment also provides a method for testing a dispersant in a sample to be tested, comprising:

[0110] 1 mL of the above filtrate was filtered through a syringe filter and then added dropwise to a 1.5 mL chromatography bottle for liquid chromatography testing;

[0111] Liquid chromatography test conditions: mobile phase composition: V (methanol): V (0.2 vol% glacial acetic acid aqueous solution) = 25:75, flow rate is 1 mL / min, UV detector wavelength is 268 nm, column oven temperature is 30°C, elution time is 28 min; after the test system is stable, 1 mL of filtrate is drawn for test analysis, and the injection volume is 20 μL.

[0112] Example 2

[0113] This embodiment provides a method for treating an electroplating solution, comprising:

[0114] Buffer solution preparation: weigh 109.2 g of anhydrous sodium acetate and 2.28 mL of glacial acetic acid solution, dilute to 1000 mL with water to obtain a buffer solution with a pH of 6;

[0115] Metal graphene electroplating solution: including dispersant sodium polynaphthalenesulfonate with a volume concentration of 20 mL / L, graphene with a mass concentration of 0.8 g / L, and nickel sulfamate with a mass concentration of 300 g / L;

[0116] Mixing reaction: In a fume hood, take 10 mL of metal graphene electroplating solution, slowly add the prepared buffer solution to 100 mL, and stir for 30 min;

[0117] Preparation of samples to be tested: The particle size distribution of graphene particles in the metal graphene electroplating solution is: D03 = 0.052 μm, D10 = 0.063 μm, D25 = 0.081 μm, D50 = 0.489 μm, D97 = 2.267 μm. Since the minimum pore size of the existing microporous filter membrane is 0.05 μm, a microporous filter membrane with a pore size of 0.05 μm is selected. The solution after the above mixed reaction is added to the filter cup for suction filtration to remove the water-insoluble solid particles therein, and the filtrate is the sample to be tested.

[0118] Accordingly, this embodiment also provides a method for testing a dispersant in a sample to be tested, comprising:

[0119] 1 mL of the above filtrate was filtered through a syringe filter and then added dropwise to a 1.5 mL chromatography bottle for liquid chromatography testing;

[0120] Liquid chromatography test conditions: mobile phase composition: V (methanol): V (0.2 vol% glacial acetic acid aqueous solution) = 15:85, flow rate is 1 mL / min, UV detector wavelength is 268 nm, column oven temperature is 30°C, elution time is 28 min; after the test system is stable, 1 mL of filtrate is drawn for test analysis, and the injection volume is 20 μL.

[0121] Example 3

[0122] This embodiment provides a method for treating an electroplating solution, comprising:

[0123] Buffer preparation: weigh 87.7 mL 0.2 mol / L NaH2PO4 and 12.3 mL 0.2 mol / L Na2HPO4 to obtain a buffer solution with a pH of 6;

[0124] Metal graphene electroplating solution: including dispersant sodium polynaphthalenesulfonate with a volume concentration of 20 mL / L, graphene with a mass concentration of 0.8 g / L, and nickel sulfamate with a mass concentration of 300 g / L;

[0125] Mixing reaction: In a fume hood, take 10 mL of metal graphene electroplating solution, slowly add the prepared buffer solution to 100 mL, and stir for 30 min;

[0126] Preparation of samples to be tested: The particle size distribution of graphene particles in the metal graphene electroplating solution is: D03 = 0.052 μm, D10 = 0.063 μm, D25 = 0.081 μm, D50 = 0.489 μm, D97 = 2.267 μm. Since the minimum pore size of the existing microporous filter membrane is 0.05 μm, a microporous filter membrane with a pore size of 0.05 μm is selected. The solution after the above mixed reaction is added to the filter cup for suction filtration to remove the water-insoluble solid particles therein, and the filtrate is the sample to be tested.

[0127] Accordingly, this embodiment also provides a method for testing a dispersant in a sample to be tested, comprising:

[0128] 1 mL of the above filtrate was filtered through a syringe filter and then added dropwise to a 1.5 mL chromatography bottle for liquid chromatography testing;

[0129] Liquid chromatography test conditions: mobile phase composition: V (methanol): V (0.2 vol% glacial acetic acid aqueous solution) = 15:85, flow rate is 1 mL / min, UV detector wavelength is 268 nm, column oven temperature is 30°C, elution time is 28 min; after the test system is stable, 1 mL of filtrate is drawn for test analysis, and the injection volume is 20 μL.

[0130] Comparative Example

[0131] This comparative example also provides a method for testing a dispersant in a sample to be tested, comprising:

[0132] 1 mL of metal graphene electroplating solution (including dispersant sodium polynaphthalenesulfonate with a volume concentration of 20 mL / L, graphene with a mass concentration of 0.8 g / L, and nickel sulfamate with a mass concentration of 300 g / L) was taken and filtered through a syringe filter, and then dropped into a 1.5 mL chromatographic bottle for liquid chromatography testing;

[0133] Liquid chromatography test conditions: mobile phase composition: V (methanol): V (0.2 vol% glacial acetic acid aqueous solution) = 25:75, flow rate is 1 mL / min, UV detector wavelength is 268 nm, column oven temperature is 30°C, elution time is 28 min; after the test system is stable, 1 mL of filtrate is drawn for test analysis, and the injection volume is 20 μL.

[0134] The volume concentrations of Examples 1 to 4 and the comparative example were calculated by integrating the chromatograms. The results are shown in Table 3.

[0135] Table 3

[0136]

[0137] As can be seen from Table 3, the plating solution is treated by the plating solution treatment method provided in the present application to obtain a sample to be tested, and the obtained sample to be tested is then subjected to liquid chromatography treatment, and the measured volume concentration of the dispersant has a high accuracy rate. This is mainly because the buffer solution changes the Zeta potential of the graphene surface in the plating solution, causing the dispersant connected to the graphene to fall off, and the dispersant will not be removed when the graphene is filtered, thereby ensuring that the content of graphene in the sample to be tested is close to or consistent with the content of graphene in the plating solution, thereby improving the accuracy of the detection of the dispersant content; while in the comparative example, no buffer solution is used, and when the graphene is removed, the dispersant attached to the graphene is removed together, so that the dispersant content in the sample to be tested is reduced, thereby affecting the accuracy of the test result.

[0138] The technical solutions provided by the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A method for treating an electroplating solution, characterized in that: The steps include: Providing a buffer solution and an electroplating solution, wherein the electroplating solution includes a dispersant and graphene; The buffer solution and the electroplating solution are mixed, and the precipitate is removed after a first filtration to obtain a sample to be tested.

2. The processing method according to claim 1, characterized in that: The buffer is an acidic buffer; and / or The buffer comprises one or more of a phosphate buffer and an acetic acid-sodium acetate buffer.

3. The processing method according to claim 2, characterized in that: The pH of the acidic buffer is 3.6 to 6; and / or The phosphate buffer is prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate; and / or The acetic acid-sodium acetate buffer is prepared from acetic acid and sodium acetate. In the acetic acid-sodium acetate buffer, the mass concentration of the sodium acetate is 5.1 g / L to 109.2 g / L, and the volume concentration of the acetic acid is 2.28 mL / L to 70 mL / L.

4. The processing method according to claim 1, characterized in that: The dispersant includes one or more of sulfonates, sulfates, and polyethers; wherein the sulfonates include one or more of sodium polynaphthalene sulfonate and sodium dodecylbenzene sulfonate; the sulfates include sodium dodecyl sulfate; the polyethers include alkylphenol polyoxyethylene ether; and / or The volume ratio of the buffer solution to the electroplating solution is (70-200):10; and / or In the electroplating solution, at least part of the dispersant is connected to the graphene; and / or The sample to be tested includes the dispersant.

5. The processing method according to claim 1, characterized in that: In the electroplating solution, the mass concentration of the graphene is 0.8 g / L; and / or The electroplating solution further comprises a metal salt, wherein the metal salt comprises a nickel salt; and / or The electroplating solution also includes a solvent.

6. The processing method according to claim 5, characterized in that: The nickel salt includes one or more of nickel sulfamate and nickel chloride; wherein the mass concentration of the nickel sulfamate is 300 g / L to 400 g / L; the mass concentration of the nickel chloride is 25 g / L to 40 g / L; and / or The solvent is selected from one or more of water, ethanol, isopropanol, N-methylpyrrolidone, dichloromethane, xylene, dichlorobenzene, ethylene glycol and toluene.

7. The processing method according to any one of claims 1 to 6, characterized in that: After mixing the buffer solution and the electroplating solution, stirring is further included, and the stirring time is 20 minutes to 50 minutes; and / or The first filtering method includes microporous membrane filtration.

8. A method for testing a dispersant in a sample to be tested, characterized in that: The steps include: Providing a sample to be tested after being treated by the electroplating solution treatment method according to any one of claims 1 to 7; The sample to be tested is subjected to a liquid chromatography test to obtain the concentration of the dispersant.

9. The testing method according to claim 8, characterized in that: The liquid chromatography test on the sample to be tested includes: after the sample to be tested is subjected to a second filtration, adding the sample to be tested to a chromatography bottle for liquid chromatography test; wherein the second filtration method is needle filter filtration.

10. The testing method according to any one of claims 8 to 9, characterized in that: The mobile phase of the liquid chromatography test comprises a mixture of methanol and glacial acetic acid aqueous solution; wherein the volume ratio of the methanol to the glacial acetic acid aqueous solution is (10-40): (60-90); and / or The flow rate of the mobile phase of the liquid chromatography test is 0.8 mL / min to 1.5 mL / min; and / or The wavelength of the ultraviolet detector of the liquid chromatography test is 268nm to 288nm; and / or The temperature of the column oven of the liquid chromatography test is 28°C to 35°C; and / or The elution time of the liquid chromatography test is 24 min to 45 min.

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