Compound dispersing agent, mixed electroplating solution and application

Abstract

The invention discloses a compound dispersing agent, a mixed electroplating solution and application, the compound dispersing agent comprises a first anionic surfactant, a second anionic surfactant and a nonionic surfactant, and the first anionic surfactant comprises a sulfonate compound; and / or the second anionic surfactant comprises one or more of betaine or carboxylate; and / or the nonionic surfactant comprises one or more of a naphthoquinone sulfonate formaldehyde condensation compound, a melamine-formaldehyde condensation compound and methylnaphthalene sulfonic acid formaldehyde condensation compound sodium salt. In the compound dispersant, the first anionic surfactant plays a role in surface wetting and dispersing, the second anionic surfactant plays a role in main dispersing, and the nonionic surfactant plays a role in surface active wetting, so that the compound dispersant disclosed by the invention has good synergism; the graphene dispersing agent plays a role in dispersing graphene in a plating solution system, plays a certain positive role in ion migration in the plating solution, and does not cause poisoning harm to the plating solution.

Description

Technical Field

[0001] The present application relates to the technical field of electroplating, and more specifically, to a compound dispersant, a mixed electroplating solution and a conductor. Background Art

[0002] Graphene is a new type of two-dimensional nanomaterial. Its nanosheets are two-dimensional materials with a single-atom layer thickness composed of sp2 hybridized carbon atoms. It is the thinnest and hardest nanomaterial known in the world, with a strength as high as 1.01 Tpa, which is 100 times that of structural steel, while its density is only 1 / 5 of that of structural steel. Its thermal conductivity coefficient is as high as 5300 W / m·K, higher than that of carbon nanotubes and diamond. At room temperature, the electron mobility exceeds 200000 cm 2 / V·S, higher than that of carbon nanotubes or silicon crystals, and its resistivity is only about 1 Ω·m, lower than that of copper or silver, making it the material with the lowest resistivity in the world.

[0003] The metal-based graphene composite electrocontact material has superior electrical conductivity, wear resistance and thermal conductivity compared with other reinforced-phase composite electrocontact materials. Graphene has good stability, so there is no problem of dielectric corrosion after the combination of graphene and metal.

[0004] Graphene has a small size and a large specific surface area, making it difficult to disperse. In addition, there is a strong π-π interaction between the graphene sheets, which makes the single-layer graphene dispersed in the dispersion liquid prone to agglomeration and form graphite, seriously affecting its performance. It is very difficult for surfactants, penetrants, etc. in the electroplating solutions of related technologies to break the π-π interaction between the graphene layers, and thus the problem that the single-layer graphene dispersed in the dispersion liquid is prone to agglomeration cannot be solved. Summary of the Invention

[0005] Based on this, the object of the present invention is to provide a compound dispersant, a mixed electroplating solution and an application, aiming to solve the problem that the single-layer graphene dispersed in the dispersion liquid in the prior art is prone to agglomeration.

[0006] The technical solution of the present application is as follows:

[0007] In the first aspect, the present application provides a compound dispersant,

[0008] The compound dispersant includes a first anionic surfactant, a second anionic surfactant and a non-ionic surfactant. The first anionic surfactant includes sulfonate compounds; and / or

[0009] The second anionic surfactant includes one or more of betaine or carboxylate; and / or

[0010] The non-ionic surfactant includes one or more of naphthoquinone sulfonic acid formaldehyde condensate, melamine-formaldehyde condensate, sodium salt of methylnaphthalene sulfonic acid formaldehyde condensate, sodium salt of cresol sulfonic acid formaldehyde condensate, and sodium salt of 2-naphthalene sulfonic acid formaldehyde condensate.

[0011] Optionally, the mass ratio of the first anionic surfactant, the second anionic surfactant and the non-ionic surfactant is (1-5):(0.5-4):(1-5).

[0012] Optionally, the sulfonate compound includes one or several of alkyl sulfonate, methylene bisnaphthalene sulfonate, alkyl benzene sulfonate, and alkyl naphthalene sulfonate; and / or

[0013] The betaine includes trimethylglycine; and / or

[0014] The carboxylate includes one or more of alkyl carboxylate and amide group polypeptide carboxylate.

[0015] Optionally, the alkyl sulfonate includes one or more of sodium diheptyl sulfosuccinate, sodium dihexyl sulfosuccinate, and sodium dodecyl diphenyl ether disulfonate; and / or

[0016] The methylene bisnaphthalene sulfonate includes one or more of sodium methylene bisnaphthalene sulfonate and potassium methylene bisnaphthalene sulfonate; and / or

[0017] The alkyl benzene sulfonate includes one or more of sodium xylene sulfonate, sodium toluene sulfonate, sodium isopropylbenzene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, and calcium xylene sulfonate; and / or

[0018] The alkyl naphthalene sulfonate includes one or more of sodium alkyl naphthalene sulfonate and sodium butyl naphthalene sulfonate; and / or

[0019] The alkyl carboxylate includes sodium stearate; and / or

[0020] The amide group polypeptide carboxylate includes sodium oleamide group polypeptide carboxylate.

[0021] In a second aspect, the present application also provides a mixed electroplating solution, which includes a compound dispersant and water, wherein the compound dispersant includes the compound dispersant described in the first aspect above.

[0022] Optionally, in the mixed electroplating solution, the mixed electroplating solution further includes stannate, copper salt, complexing agent, and alkali metal hydroxide.

[0023] Optionally, in the mixed electroplating solution,

[0024] The mass concentration of the first anionic surfactant is 1-5 g / L; and / or

[0025] The mass concentration of the second anionic surfactant is 0.5 - 4 g / L; and / or

[0026] The mass concentration of the nonionic surfactant is 1 - 5 g / L and / or

[0027] The mass concentration of the graphene is 0.5 - 2 g / L; and / or

[0028] The mass concentration of the stannate is 85 - 130 g / L; and / or

[0029] The mass concentration of the copper salt is 5 - 20 g / L; and / or

[0030] The mass concentration of the complexing agent is 10 - 25 g / L; and / or

[0031] The mass concentration of the alkali metal hydroxide is 5 - 15 g / L.

[0032] Optionally, in the mixed electroplating solution, the stannate includes one or more of sodium stannate and its hydrates; and / or

[0033] The copper salt includes cuprous cyanide; and / or

[0034] The complexing agent includes one or more of potassium cyanide and sodium cyanide; and / or

[0035] The alkali metal hydroxide includes one or more of potassium hydroxide and sodium hydroxide.

[0036] Optionally, when electroplating with the mixed electroplating solution, the temperature is 45 - 65 °C; and / or

[0037] The current density is 0.5 - 1.5 A / dm 2 .

[0038] In a third aspect, the present application also provides a conductor, including a substrate and a coating located outside the substrate, and the coating is prepared from the mixed electroplating solution described in the second aspect above.

[0039] The present application has the following beneficial effects:

[0040] In the compound dispersant of this application, the first anionic surfactant plays a role in surface wetting and dispersion, the second anionic surfactant plays a main dispersion role, and the non-ionic surfactant plays a role in surface active wetting. The compound dispersant of this application has good synergistic cooperation, plays a role in dispersing graphene in the plating solution system, and has a certain positive effect on the ion migration in the plating solution, and will not cause poisoning hazards to the plating solution. In addition, the compound dispersant of this application also has a certain wetting effect on the cathode. In addition, the compound dispersant of this application can make hydrogen bubbles more easily detach from the electroplated part, thereby reducing vacuum, and can wet graphene, facilitating the dispersant to play a role. Under the action of the dispersant, graphene can be repelled and dispersed from each other, facilitating electroplating. Specific embodiments

[0041] Next, the technical solutions in the embodiments of this application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of this application. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of this application.

[0042] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art, and the materials or reagents used in the embodiments and comparative examples of this application are commercially available. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred methods and materials described herein are for illustrative purposes only and do not limit the content of this application.

[0043] It should be noted that the description order of the following embodiments does not limit the preferred order of the embodiments. The various embodiments of this application can exist in a range form; it should be understood that the description in a range form is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the present invention; therefore, it should be considered that the described range description has specifically disclosed all possible sub-ranges and single values within that range. For example, it should be considered that the range description from 1 to 6 has 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., and single numbers within the counted range, such as 1, 2, 3, 4, 5, and 6, which applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0044] In the description of this application, the term "comprising" means "including but not limited to".

[0045] The terms "multiple", "many times" or similar expressions refer to two or more, for example, it can be two, three, four, five, six, etc.

[0046] The selection scope of the term "and / or" includes any one of two or more related listed items, and also includes any and all combinations of the related listed items. The said any and all combinations include combinations of any two related listed items, any more related listed items, or all related listed items. For example, "A and / or B" includes three parallel solutions: A, B, and A + B. Another example, for the technical solution of "A, and / or, B, and / or, C, and / or, D", it includes any one of A, B, C, and D (that is, the technical solutions connected by "logical or"), and also includes any and all combinations of A, B, C, and D. That is, it includes combinations of any two or any three of A, B, C, and D, and also includes the four-item combination of A, B, C, and D (that is, the technical solutions connected by "logical and").

[0047] The term "solid content" refers to the proportion of the mass of the solids in the slurry to the total mass of the slurry.

[0048] The technical solutions of the present application are as follows:

[0049] In a first aspect, the embodiments of the present application provide a compound dispersant. The three components cooperate with each other to effectively block or slow down the agglomeration of graphene in the dispersion liquid, and the whole system has good stability. The compound dispersant includes a first anionic surfactant, a second anionic surfactant, and a non-ionic surfactant, wherein,

[0050] In some embodiments, the first anionic surfactant can be selected from, but not limited to, sulfonate compounds.

[0051] In some embodiments, the second anionic surfactant includes one or more of betaine or carboxylate.

[0052] In some embodiments, the non-ionic surfactant includes one or more of sulfonated naphthoquinone formaldehyde condensate, melamine-formaldehyde condensate, sodium salt of methylnaphthalenesulfonic acid formaldehyde condensate, sodium salt of cresol sulfonic acid formaldehyde condensate, and sodium salt of 2-naphthalene-sulfonic acid formaldehyde condensate.

[0053] In the prior art, although some dispersants can disperse graphene well in water, they cannot effectively disperse graphene in the plating solution. The plating solution is a solution system containing different ions and compounds, and different ions and compounds will have a certain impact on the addition of the dispersant to the plating solution, which may cause the dispersant to lose its original dispersing function.

[0054] In the present application, the first anionic surfactant plays a role in surface wetting and dispersion, the second anionic surfactant plays a main dispersion role, and the nonionic surfactant plays a surface-active wetting role. The compound dispersant of the present application has good synergistic cooperation, plays a role in dispersing graphene in the plating solution system, and has a certain positive effect on the ion migration in the plating solution, and will not cause poisoning hazards to the plating solution. In addition, the compound dispersant of the present application also has a certain wetting effect on the cathode. In addition, the compound dispersant of the present application can make hydrogen bubbles more easily detach from the electroplated part, thereby reducing the vacuum, and can wet graphene, facilitating the action of the dispersant. Under the action of the dispersant, graphene can be repelled and dispersed from each other, facilitating electroplating.

[0055] In some embodiments, the anionic surfactant includes a first anionic surfactant and a second anionic surfactant, and the mass ratio of the first anionic surfactant, the second anionic surfactant and the nonionic surfactant is (1-5):(0.5-4):(1-5). For example, it is 1:0.5:1, 1:2:3, 1:3:4, 1:4:5, 2:0.5:1, 2:1.5:2, 2:3:4, 2:4:5, 3:0.5:1, 3:1:2, 3:2:3, 3:3:4, 3:4:5, 4:0.5:1, 4:1:1, 4:2:2, 4:2:3, 4:3:4, 4:4:5, 5:0.5:1, 5:1:1, 5:2:2, 5:2:3, 5:3:4, 5:4:5 or a value between any two of the foregoing values. Within the range of the mass ratio, a compound dispersant that can effectively block or slow down the agglomeration of graphene in the dispersion liquid can be obtained, and the compound dispersant system is stable.

[0056] In some embodiments, the first anionic surfactant can be selected from, but not limited to, sulfonate compounds.

[0057] The sulfonate compounds can be selected from, but not limited to, one or several of alkyl sulfonates, methylene bisnaphthalene sulfonates, alkyl benzene sulfonates, and alkyl naphthalene sulfonates.

[0058] The alkyl sulfonates include one or more of sodium diheptyl sulfosuccinate, sodium dihexyl sulfosuccinate, and sodium dodecyl diphenyl ether disulfonate.

[0059] The methylene bisnaphthalene sulfonates include one or more of sodium methylene bisnaphthalene sulfonate or potassium methylene bisnaphthalene sulfonate.

[0060] The alkyl benzene sulfonates include one or more of sodium xylene sulfonate, sodium toluene sulfonate, sodium isopropyl benzene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, and calcium xylene sulfonate.

[0061] The alkylnaphthalenesulfonate includes one or more of sodium alkylnaphthalenesulfonate and sodium butylnaphthalenesulfonate.

[0062] In some embodiments, the second anionic surfactant includes one or more of betaine or carboxylate.

[0063] The betaine includes trimethylglycine.

[0064] The carboxylate includes one or more of alkyl carboxylate and amide group polypeptide carboxylate.

[0065] The alkyl carboxylate includes sodium stearate.

[0066] The amide group polypeptide carboxylate includes sodium oleamide group polypeptide carboxylate.

[0067] In a second aspect, an embodiment of the present application further provides a mixed electroplating solution, which includes a compound dispersant, water, and graphene. Among them, the compound dispersant includes the compound dispersant described in the first aspect above.

[0068] In some embodiments, the mixed electroplating solution further includes stannate, copper salt, complexing agent, and alkali metal hydroxide.

[0069] The mixed electroplating solution of the present application improves the dispersibility of graphene in the copper-tin electroplating solution, so that the graphene after electroplating is evenly distributed on the coating and the copper-tin alloy is evenly distributed, improving the conductivity and wear resistance of the electroplated part.

[0070] In some embodiments, in the mixed electroplating solution, the mass concentration of the first anionic surfactant is 1-5 g / L. For example, it is 1 g / L, 1.5 g / L, 2 g / L, 2.6 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L, or a value between any two of the foregoing values.

[0071] In some embodiments, in the mixed electroplating solution, the mass concentration of the second anionic surfactant is 0.5-4 g / L. For example, it is 0.5 g / L, 0.8 g / L, 1 g / L, 1.2 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 2.5 g / L, 2.8 g / L, 3 g / L, 3.2 g / L, 3.5 g / L, 3.8 g / L, 4 g / L, or a value between any two of the foregoing values.

[0072] In some embodiments, in the mixed electroplating solution, the mass concentration of the non-ionic surfactant is 1-5 g / L. For example, it is 1 g / L, 1.2 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 2.2 g / L, 2.5 g / L, 2.8 g / L, 3 g / L, 3.3 g / L, 3.5 g / L, 3.8 g / L, 4 g / L, 4.2 g / L, 4.5 g / L, 4.8 g / L, 5 g / L or a value between any two of the foregoing values.

[0073] In some embodiments, in the mixed electroplating solution, the mass volume concentration of the graphene is 0.5-2 g / L. For example, it is 0.5 g / L, 0.8 g / L, 1 g / L, 1.2 g / L, 1.4 g / L, 1.6 g / L, 1.8 g / L, 2 g / L or a value between any two of the foregoing values.

[0074] In some embodiments, in the mixed electroplating solution, the mass volume concentration of the stannate is 85-130 g / L. For example, it is 85 g / L, 90 g / L, 95 g / L, 100 g / L, 105 g / L, 110 g / L, 115 g / L, 120 g / L, 125 g / L, 130 g / L or a value between any two of the foregoing values.

[0075] In some embodiments, in the mixed electroplating solution, the mass volume concentration of the copper salt is 5-20 g / L. For example, it is 5 g / L, 8 g / L, 10 g / L, 12 g / L, 15 g / L, 17 g / L, 18 g / L, 20 g / L or a value between any two of the foregoing values.

[0076] In some embodiments, in the mixed electroplating solution, the mass volume concentration of the complexing agent is 10-25 g / L. For example, it is 10 g / L, 12 g / L, 16 g / L, 18 g / L, 20 g / L, 22 g / L, 23 g / L, 25 g / L or a value between any two of the foregoing values.

[0077] In some embodiments, in the mixed electroplating solution, the mass volume concentration of the alkali metal hydroxide is 5-15 g / L. For example, it is 5 g / L, 8 g / L, 10 g / L, 12 g / L, 13 g / L, 15 g / L or a value between any two of the foregoing values.

[0078] In some embodiments, the stannate includes one or more of sodium stannate and its hydrates. Preferably, the stannate includes sodium stannate trihydrate.

[0079] In some embodiments, the copper salt includes cuprous cyanide.

[0080] In some embodiments, the complexing agent includes one or more of potassium cyanide and sodium cyanide.

[0081] In some embodiments, the alkali metal hydroxide includes one or more of potassium hydroxide and sodium hydroxide.

[0082] In some embodiments, the temperature of the mixed electroplating solution during electroplating is 45 to 65 °C. For example, it is 45 °C, 48 °C, 50 °C, 52 °C, 54 °C, 56 °C, 58 °C, 60 °C, 64 °C, 65 °C or a value between any two of the foregoing values.

[0083] In some embodiments, the current density of the mixed electroplating solution during electroplating is 0.5 to 1.5 A / dm 2 . For example, it is 0.5 A / dm 2 , 0.6 A / dm 2 , 0.8 A / dm 2 , 1 A / dm 2 , 1.2 A / dm 2 , 1.3 A / dm 2 , 1.5 A / dm 2 .

[0084] In a third aspect, an embodiment of the present application further provides a conductor, including a substrate and a coating located outside the substrate, and the coating is prepared from the mixed electroplating solution described in the second aspect above.

[0085] The following specifically illustrates the present application through specific embodiments. The following embodiments are only partial embodiments of the present application and do not limit the present application.

[0086] Example 1

[0087] This example provides a compound dispersant, which is composed of distilled water, a first anionic surfactant, a second anionic surfactant, and a nonionic surfactant; the first anionic surfactant includes sulfonate compounds, the sulfonate compounds include alkyl sulfonates, and the alkyl sulfonates include sodium diheptyl sulfosuccinate; the second anionic surfactant includes betaine, and the betaine includes trimethylglycine; the nonionic surfactant includes sulfonated naphthoquinone formaldehyde condensate; in the compound dispersant, the mass fraction of the first anionic surfactant is 3%, the mass fraction of the second anionic surfactant is 2.25%, the mass fraction of the nonionic surfactant is 3%, and the balance is distilled water.

[0088] In this example, the preparation method of the compound dispersant is prepared according to the conventional method in the art.

[0089] Example 2

[0090] This example is basically the same as Example 1, except that in the compound dispersant, the mass fraction of the first anionic surfactant is 1%, the mass fraction of the second anionic surfactant is 0.5%, the mass fraction of the nonionic surfactant is 1%, and the balance is distilled water.

[0091] Example 3

[0092] This example is basically the same as Example 1, except that in the compound dispersant, the mass fraction of the first anionic surfactant is 5%, the mass fraction of the second anionic surfactant is 4%, the mass fraction of the nonionic surfactant is 5%, and the balance is distilled water.

[0093] Example 4

[0094] This example is basically the same as Example 1, except that the first anionic surfactant includes sulfonate compounds, the sulfonate compounds include alkyl sulfonates, and the alkyl sulfonates include sodium dihexyl sulfosuccinate; the second anionic surfactant includes carboxylates, the carboxylates include alkyl carboxylates, and the alkyl carboxylates include sodium stearate; the nonionic surfactant includes melamine-formaldehyde condensate.

[0095] Example 5

[0096] This example is basically the same as Example 1, except that the first anionic surfactant includes sulfonate compounds, the sulfonate compounds include alkyl sulfonates, and the alkyl sulfonates include sodium dodecyl diphenyl ether disulfonate; the second anionic surfactant includes carboxylates, the carboxylates include amide group polypeptide carboxylates, and the amide group polypeptide carboxylates include sodium oleamide polypeptide carboxylate; the nonionic surfactant includes melamine-formaldehyde condensate.

[0097] Example 6

[0098] This example is basically the same as Example 1, except that the first anionic surfactant includes sulfonate compounds, the sulfonate compounds include methylene bisnaphthalene sulfonates, and the methylene bisnaphthalene sulfonates include sodium methylene bisnaphthalene sulfonate; the second anionic surfactant includes carboxylates, the carboxylates include amide group polypeptide carboxylates, and the amide group polypeptide carboxylates include sodium oleamide polypeptide carboxylate; the nonionic surfactant includes sodium methylnaphthalene sulfonate formaldehyde condensate.

[0099] Example 7

[0100] This embodiment is basically the same as Embodiment 1, except that the first anionic surfactant includes sulfonate compounds, the sulfonate compounds include alkylbenzene sulfonates, and the alkylbenzene sulfonates include sodium xylene sulfonate; the second anionic surfactant includes carboxylates, the carboxylates include alkyl carboxylates, and the alkyl carboxylates include sodium stearate; the nonionic surfactant includes sodium salt of cresol sulfonic acid formaldehyde condensate.

[0101] Embodiment 8

[0102] This embodiment is basically the same as Embodiment 1, except that the first anionic surfactant includes sulfonate compounds, the sulfonate compounds include alkylbenzene sulfonates, and the alkylbenzene sulfonates include ammonium xylene sulfonate; the second anionic surfactant includes carboxylates, the carboxylates include amide group polypeptide carboxylates, and the amide group polypeptide carboxylates include sodium oleoyl polypeptide carboxylate; the nonionic surfactant includes sodium salt of 2-naphthalene sulfonic acid formaldehyde condensate.

[0103] The following are the implementation manners of the mixed electroplating solution of the present invention.

[0104] Electroplating Solution Embodiment 1

[0105] The mixed electroplating solution of this embodiment includes a first anionic surfactant, a second anionic surfactant, a nonionic surfactant, water, graphene, stannate, copper salt, complexing agent and alkali metal hydroxide; in the mixed electroplating solution, the first anionic surfactant is sodium diheptyl sulfosuccinate, and its content is 3 g / L, the second anionic surfactant is trimethylglycine, and its content is 2.25 g / L, the nonionic surfactant is naphthoquinone sulfonic acid formaldehyde condensate, and its content is 3 g / L, the mass volume concentration of the graphene is 1.25 g / L, the mass volume concentration of the stannate is 107 g / L, the mass volume concentration of the copper salt is 12 g / L, the mass volume concentration of the complexing agent is 17 g / L, and the mass volume concentration of the alkali metal hydroxide is 10 g / L; the stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes potassium cyanide, and the alkali metal hydroxide includes sodium hydroxide.

[0106] The preparation method of the mixed electroplating solution is prepared according to the conventional method in the art.

[0107] Electroplating Solution Embodiment 2

[0108] This example is basically the same as Example 1 of the electroplating solution, except that in the mixed electroplating solution, the first anionic surfactant is sodium diheptyl sulfosuccinate with a content of 1 g / L, the second anionic surfactant is trimethylglycine with a content of 0.5 g / L, the non-ionic surfactant is sulfonated naphthoquinone formaldehyde condensate with a content of 1 g / L, the mass-volume concentration of the graphene is 0.5 g / L, the mass-volume concentration of the stannate is 85 g / L, the mass-volume concentration of the copper salt is 5 g / L, the mass-volume concentration of the complexing agent is 10 g / L, and the mass-volume concentration of the alkali metal hydroxide is 5 g / L; the stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes potassium cyanide, and the alkali metal hydroxide includes potassium hydroxide.

[0109] Electroplating Solution Example 3

[0110] This example is basically the same as Example 1 of the electroplating solution, except that in the mixed electroplating solution, the first anionic surfactant is sodium diheptyl sulfosuccinate with a content of 5 g / L, the second anionic surfactant is trimethylglycine with a content of 4 g / L, the non-ionic surfactant is sulfonated naphthoquinone formaldehyde condensate with a content of 5 g / L, the mass-volume concentration of the graphene is 2 g / L, the mass-volume concentration of the stannate is 130 g / L, the mass-volume concentration of the copper salt is 20 g / L, the mass-volume concentration of the complexing agent is 25 g / L, and the mass-volume concentration of the alkali metal hydroxide is 15 g / L; the stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes sodium cyanide, and the alkali metal hydroxide includes sodium hydroxide.

[0111] Electroplating Solution Example 4

[0112] The mixed electroplating solution of this example includes a first anionic surfactant, a second anionic surfactant, a non-ionic surfactant, water, graphene, stannate, copper salt, complexing agent, and alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium dihexyl sulfosuccinate with a content of 3.5 g / L, the second anionic surfactant is sodium stearate with a content of 2.5 g / L, the non-ionic surfactant is melamine-formaldehyde condensate with a content of 3.2 g / L, the mass-volume concentration of the graphene is 0.8 g / L, the mass-volume concentration of the stannate is 108 g / L, the mass-volume concentration of the copper salt is 10 g / L, the mass-volume concentration of the complexing agent is 15 g / L, and the mass-volume concentration of the alkali metal hydroxide is 10 g / L; the stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes potassium cyanide, and the alkali metal hydroxide includes potassium hydroxide.

[0113] Electroplating Solution Example 5

[0114] The mixed electroplating solution of this embodiment includes a first anionic surfactant, a second anionic surfactant, a non-ionic surfactant, water, graphene, stannate, copper salt, complexing agent and alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium dodecyl diphenyl ether disulfonate with a content of 3 g / L, the second anionic surfactant is sodium oleoyl polypeptide carboxylate with a content of 2 g / L, the non-ionic surfactant is melamine-formaldehyde condensate with a content of 3.5 g / L, the mass-volume concentration of the graphene is 1 g / L, the mass-volume concentration of the stannate is 102 g / L, the mass-volume concentration of the copper salt is 12 g / L, the mass-volume concentration of the complexing agent is 14 g / L, and the mass-volume concentration of the alkali metal hydroxide is 9 g / L; the stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes sodium cyanide, and the alkali metal hydroxide includes sodium hydroxide.

[0115] Electroplating Solution Example 6

[0116] The mixed electroplating solution of this embodiment includes a first anionic surfactant, a second anionic surfactant, a non-ionic surfactant, water, graphene, stannate, copper salt, complexing agent and alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium methylene bisnaphthalene sulfonate with a content of 3 g / L, the second anionic surfactant is sodium oleoyl polypeptide carboxylate with a content of 2 g / L, the non-ionic surfactant is sodium methylnaphthalene sulfonate formaldehyde condensate with a content of 3.5 g / L, the mass-volume concentration of the graphene is 0.8 g / L, the mass-volume concentration of the stannate is 106 g / L, the mass-volume concentration of the copper salt is 12 g / L, the mass-volume concentration of the complexing agent is 13 g / L, and the mass-volume concentration of the alkali metal hydroxide is 8 g / L; the stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes sodium cyanide, and the alkali metal hydroxide includes sodium hydroxide.

[0117] Electroplating Solution Example 7

[0118] The mixed electroplating solution of this embodiment includes a first anionic surfactant, a second anionic surfactant, a non-ionic surfactant, water, graphene, stannate, copper salt, complexing agent, and alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium xylene sulfonate, and its content is 3.2 g / L; the second anionic surfactant is sodium stearate, and its content is 2.2 g / L; the non-ionic surfactant is sodium cresol sulfonic acid formaldehyde condensate, and its content is 2.8 g / L; the mass-volume concentration of the graphene is 1.1 g / L; the mass-volume concentration of the stannate is 108 g / L; the mass-volume concentration of the copper salt is 10 g / L; the mass-volume concentration of the complexing agent is 14 g / L; the mass-volume concentration of the alkali metal hydroxide is 10 g / L. The stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes potassium cyanide, and the alkali metal hydroxide includes potassium hydroxide.

[0119] Electroplating Solution Example 8

[0120] The mixed electroplating solution of this embodiment includes a first anionic surfactant, a second anionic surfactant, a non-ionic surfactant, water, graphene, stannate, copper salt, complexing agent, and alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is ammonium xylene sulfonate, and its content is 2.8 g / L; the second anionic surfactant is sodium oleoyl polypeptide carboxylate, and its content is 2.5 g / L; the non-ionic surfactant is sodium 2-naphthalene sulfonic acid formaldehyde condensate, and its content is 3.6 g / L; the mass-volume concentration of the graphene is 1.2 g / L; the mass-volume concentration of the stannate is 100 g / L; the mass-volume concentration of the copper salt is 15 g / L; the mass-volume concentration of the complexing agent is 16 g / L; the mass-volume concentration of the alkali metal hydroxide is 9 g / L. The stannate includes sodium stannate trihydrate, the copper salt includes cuprous cyanide, the complexing agent includes potassium cyanide, and the alkali metal hydroxide includes potassium hydroxide.

[0121] Comparative Example 1

[0122] Commercially available pure iron parts.

[0123] Comparative Example 2

[0124] This comparative example is basically the same as Electroplating Solution Example 1, except that the compound dispersant and graphene in the mixed electroplating solution are removed.

[0125] Comparative Example 3

[0126] This comparative example is basically the same as Electroplating Solution Example 1, except that the compound dispersant in Electroplating Solution Example 1 is replaced with sodium 2-ethylhexyl sulfate, which is conventional in the art.

[0127] Comparative Example 4

[0128] This comparative example is basically the same as Example 1 of the electroplating solution, except that the compound dispersant in Example 1 of the electroplating solution is replaced with sodium dioctyl sulfosuccinate, which is conventional in the art.

[0129] The temperature during electroplating is 55 °C, and the current density is 1 A / dm 2 After electroplating, the Vickers hardness of the silver is tested. To eliminate the interference of the iron matrix metal on the hardness test of the coating, the thickness of the metal coating in the experimental test is greater than 30 microns; the micro-resistance is tested by a precision four-probe resistivity tester; the wear resistance is tested by detecting the coating with a steel wool friction tester, measuring the mass before and after every 5000 times of friction, and calculating the wear rate through the mass difference; the test method of Zeta potential is electrophoresis method to measure the dispersion uniformity of the plating solution, and the test results are shown in Table 1.

[0130] Table 1

[0131]

[0132]

[0133] Note: The wear resistance is the average number of times that can be endured per micron, and the unit is / times.

[0134] As can be seen from Table 1, compared with Comparative Examples 2 and 3, the absolute value of the Zeta potential of the electroplating solutions of Examples 1-8 of the electroplating solution of the present application is higher than that of Comparative Examples 2 and 3, indicating that the graphene in the electroplating solution added with the compound dispersant of the present application has good dispersion; the hardness of the products plated with the electroplating solutions of Examples 1-8 of the present application is higher than that of Comparative Examples 1-4, indicating that the products plated with the electroplating solution added with the compound dispersant of the present application have high hardness; the micro-resistance of the products plated with the electroplating solutions of Examples 1-8 of the present application is less than that of Comparative Examples 1-4, indicating that the products plated with the electroplating solution of the compound dispersant of the present application have good conductivity; the average wear rate of the products plated with the electroplating solutions of Examples 1-8 of the present application per 5000 times is less than that of Comparative Examples 2-4, indicating that the coating of the products plated with the electroplating solution of the compound dispersant of the present application has good wear resistance. This is because Comparative Example 1 is a pure iron piece, Comparative Example 2 is only copper-tin plated, and Comparative Examples 3 and 4 are conventional dispersants in the art, and the graphene in the electroplating solution has poor dispersion.

[0135] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and not to limit them; although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: still can modify the specific implementation manners of the present application or make equivalent replacements for some technical features; without departing from the spirit of the technical solutions of the present application, they should all be covered by the scope of the technical solutions claimed in the present application.

Claims

1. A compound dispersant, characterized in that, The compound dispersant includes a first anionic surfactant, a second anionic surfactant and a nonionic surfactant. The first anionic surfactant includes sulfonate compounds; and / or The second anionic surfactant includes one or more of betaine or carboxylate; and / or The nonionic surfactant includes one or more of sulfonated naphthoquinone formaldehyde condensate, melamine-formaldehyde condensate, sodium salt of methylnaphthalenesulfonic acid formaldehyde condensate, sodium salt of cresol sulfonic acid formaldehyde condensate, sodium salt of 2-naphthalenesulfonic acid formaldehyde condensate.

2. The compound dispersant according to claim 1, characterized in that, The mass ratio of the first anionic surfactant, the second anionic surfactant and the nonionic surfactant is (1-5):(0.5-4):(1-5).

3. The compound dispersant according to claim 1, wherein The sulfonate compounds include one or several of alkyl sulfonates, methylene bisnaphthalene sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates; and / or The betaine includes trimethylglycine; and / or The carboxylate includes one or more of alkyl carboxylates, amide group polypeptide carboxylates.

4. The compound dispersant according to claim 3, wherein The alkyl sulfonates include one or more of sodium diheptyl sulfosuccinate, sodium dihexyl sulfosuccinate and sodium dodecyl diphenyl ether disulfonate; and / or The methylene bisnaphthalene sulfonates include one or more of sodium methylene bisnaphthalene sulfonate or potassium methylene bisnaphthalene sulfonate; and / or The alkylbenzene sulfonates include one or more of sodium xylene sulfonate, sodium toluene sulfonate, sodium isopropylbenzene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate; and / or The alkylnaphthalene sulfonates include one or more of sodium alkylnaphthalene sulfonate and sodium butylnaphthalene sulfonate; and / or The alkyl carboxylates include sodium stearate; and / or The amide group polypeptide carboxylates include sodium oleoyl polypeptide carboxylate.

5. A mixed electroplating solution, characterized in that, The mixed electroplating solution includes a compound dispersant, water, graphene, wherein the compound dispersant includes the compound dispersant according to any one of claims 1-4.

6. The mixed electroplating solution according to claim 5, wherein, The mixed electroplating solution further includes stannate, copper salt, complexing agent and alkali metal hydroxide.

7. The mixed electroplating solution according to claim 6, characterized in that, In the mixed electroplating solution, The mass concentration of the first anionic surfactant is 1-5 g / L; and / or The mass concentration of the second anionic surfactant is 0.5-4 g / L; and / or The mass concentration of the nonionic surfactant is 1-5 g / L and / or The mass concentration of the graphene is 0.5-2 g / L; and / or The mass concentration of the stannate is 85-130 g / L; and / or The mass concentration of the copper salt is 5-20 g / L; and / or The mass concentration of the complexing agent is 10-25 g / L; and / or The mass concentration of the alkali metal hydroxide is 5-15 g / L.

8. The mixed electroplating solution according to claim 6, wherein In the mixed electroplating solution, the stannate includes one or more of sodium stannate and its hydrates; and / or The copper salt includes cuprous cyanide; and / or The complexing agent includes one or more of potassium cyanide and sodium cyanide; and / or The alkali metal hydroxide includes one or more of potassium hydroxide and sodium hydroxide.

9. The mixed electroplating solution according to claim 6, characterized in that, The temperature during electroplating with the mixed electroplating solution is 45-65 °C; and / or The current density is 0.5 to 1.5 A / dm 2 .

10. A conductor, characterized in that, It includes a substrate and a coating located outside the substrate, and the coating is prepared from the mixed electroplating solution according to any one of claims 5-9 above.

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