Electroplating additive solution, preparation method and hard silver graphene electroplating mixed solution

Abstract

The invention discloses an electroplating additive solution, a preparation method and a hard silver graphene electroplating mixed solution. The electroplating additive comprises metal oxide, oleate, alkali metal hydroxide and water. When the electroplating additive solution provided by the invention is used in an electroplating mixed solution, the metal oxide can stably and reliably refine the crystal of a plating layer and improve the polarization reaction of a cathode, so that the hardness of the finally formed plating layer is increased. According to the electroplating mixed solution, the alkali metal hydroxide can react with oleate, and a product obtained through the reaction can be complexed with the metal oxide, so that the metal oxide cannot be precipitated in the electroplating mixed solution, later electroplating is facilitated, further, when the electroplating mixed solution is used for manufacturing a plated part, the metal oxide can be uniformly dispersed in a plating layer, and the overall hardness of the plating layer is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of electroplating, and in particular to an electroplating additive solution and a preparation method thereof, and a hard silver graphene electroplating mixed solution. Background Art

[0002] Traditional connectors are usually plated with a silver layer. With the development of technology, electroplating a silver-graphene mixed coating on the outside of the connector has become a better choice, which can further improve the conductivity of the connector. However, the number of plug-in and unplug times of the connector is high, and the hardness of the existing silver-graphene coating is low, which reduces the life of the connector. There is an urgent need for a silver-graphene coating with high hardness and good conductivity to solve this problem. Summary of the invention

[0003] In view of this, the present invention provides an electroplating additive solution and a preparation method, and a hard silver graphene electroplating mixed solution, aiming to improve the problem of low hardness of the existing silver graphene coating.

[0004] The embodiment of the present invention is implemented as follows: an electroplating additive solution includes a metal oxide, an oleate, an alkali metal hydroxide, and water;

[0005] The mass ratio of the metal oxide, oleate, alkali metal hydroxide and water is 1:(1-4):(3-6):(25-60).

[0006] Optionally, in some embodiments, the metal oxide includes one or more of antimony oxide, bismuth oxide, and manganese oxide.

[0007] Optionally, in some embodiments, the alkali metal hydroxide includes one or more of sodium hydroxide and potassium hydroxide.

[0008] Optionally, in some embodiments, the oleic acid ester includes one or more of trimethylolpropane oleate, pentaerythritol oleate, isooctyl oleate, and neopentyl glycol dioleate.

[0009] Accordingly, an embodiment of the present invention further provides a method for preparing the electroplating additive solution as described above, comprising:

[0010] mixing an alkali metal hydroxide and an oleic acid ester, and stirring to obtain a first solution;

[0011] adding a metal oxide and water to the first solution, stirring and heating to obtain a second solution;

[0012] The second solution is allowed to stand, and the upper clear liquid is taken as the electroplating additive solution.

[0013] Optionally, in some embodiments, the stirring time of the first solution is 5-15 minutes;

[0014] The heating time of the second solution is 4-6 hours, and the heating temperature is 70-85° C.;

[0015] The second solution is allowed to stand for 4-6 hours.

[0016] Correspondingly, an embodiment of the present invention further provides a hard silver graphene electroplating mixed solution comprising the electroplating additive solution as described above, characterized in that:

[0017] The electroplating mixed solution also includes silver salt, complexing agent, graphene and dispersant.

[0018] Optionally, in some embodiments, the silver salt comprises potassium silver cyanide; and / or

[0019] The complexing agent includes one or more of potassium cyanide and sodium cyanide; and / or

[0020] The dispersant includes one or more of aminosalicylic acid salt, polyparahydroxybenzoic acid ester and polyacrylic acid salt.

[0021] Optionally, in some embodiments, the concentration of the silver salt in the electroplating mixture is 40-60 g / L; and / or

[0022] In the electroplating mixed solution, the concentration of the complexing agent is 100-200 g / L; and / or

[0023] In the electroplating mixed solution, the concentration of the graphene is 1-3 g / L; and / or

[0024] In the electroplating mixed solution, the concentration of the dispersant is 0.5-3.9 g / L; and / or

[0025] In the electroplating mixed solution, the concentration of the electroplating additive solution is 7-12 ml / L.

[0026] Optionally, in some embodiments, the dispersant includes sodium aminosalicylate at a concentration of 0.1-1 g / L, polyparaben at a concentration of 0.1-2 g / L, and sodium polyacrylate at a concentration of 0.3-0.9 g / L.

[0027] The electroplating additive of the present invention includes metal oxide and oleic acid ester. When the metal oxide is used in the electroplating mixed solution, the metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. The alkali metal hydroxide can react with the oleic acid ester, and the product obtained by the reaction can be complexed with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixed solution, which is convenient for later electroplating.

[0028] In addition, the electroplating mixture of the present invention contains graphene and a dispersant. After the aforementioned electroplating additive is added to the electroplating mixture, the oleate can also lubricate the graphene surface to prevent the graphene from agglomerating. The oleate and the dispersant also have a synergistic effect. The two synergistically disperse the graphene and the metal oxide, which not only reduces the amount of the dispersant, but also enables each ion, metal oxide and graphene to reach an ideal migration rate in the electroplating mixture, thereby facilitating the preparation of a coating with excellent thermal conductivity, electrical conductivity and hardness. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, 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 invention. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 The present invention provides a flow chart of a method for preparing an electroplating additive solution. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those skilled in the art without creative work belong to the scope of protection of the present invention. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0032] In the description of the present invention, the term "including" means "including but not limited to." The terms first, second, third, etc. are used merely as labels and do not impose numerical requirements or establish a sequence.

[0033] In the present invention, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B may represent: A exists alone, A and B exist at the same time, and B exists alone. A and B may be singular or plural.

[0034] In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one", "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.

[0035] Various embodiments of the present invention 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 invention; 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.

[0036] The technical solution of the present invention is as follows:

[0037] In a first aspect, an embodiment of the present invention provides an electroplating additive solution, which is mainly used in a hard silver graphene electroplating mixture to improve the hardness of a coating prepared using the electroplating mixture.

[0038] The electroplating additive solution of the present invention comprises metal oxide, oleate, alkali metal hydroxide and water. Among them, the metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. Optionally, the metal oxide includes but is not limited to one or more of antimony oxide, bismuth oxide, and manganese oxide. Alkali metal hydroxide can react with oleate, and the product obtained by the reaction will be complexed with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixture, which is convenient for later electroplating. Optionally, alkali metal hydroxide includes but is not limited to one or more of sodium hydroxide and potassium hydroxide. Optionally, oleate includes one or more of trimethylolpropane oleate, pentaerythritol oleate, isooctyl oleate, and neopentyl glycol dioleate. When the electroplating mixture is used to make a plated part, silver ions, metal oxides and graphene can be synchronized and migrated in proportion, so that the silver ions, metal oxides and graphene can be evenly dispersed in the coating, thereby improving the hardness of the coating as a whole.

[0039] In the electroplating additive solution, the mass ratio of metal oxide, oleate, alkali metal hydroxide and water is 1:(1-4):(3-6):(25-60), for example, 1:(2-3):(3-4):(50-60), 1:(1-2):(3-5):(30-40), 1:(3-4):(4-6):(40-55), 1:(1.3-2.2):(4-5):(25-40), 1:(2.8-3.5):(3-6):(35-50), 1:(1.2-1.8):(3.5-5):(37-52), 1:(3.3-3.9):(4-4.5):(40-60), etc. Within the aforementioned ratio range, when the electroplating additive is used in the hard silver graphene electroplating mixture, the reaction product of the alkali metal hydroxide and the oleic acid ester can fully prevent the precipitation of the metal oxide, and the oleic acid ester has good dispersion properties, which is beneficial for the oleic acid ester to disperse the metal oxide and the silver ions, metal oxide and graphene to migrate synchronously in proportion. The metal oxide can be evenly distributed in the coating and can stably and reliably refine the coating crystals, thereby increasing the hardness of the coating finally formed.

[0040] Second, see Figure 1 The present invention also provides a method for preparing an electroplating additive solution, comprising the following steps:

[0041] Step S100, mixing 3-6 parts of alkali metal hydroxide and 1-4 parts of oleate, and stirring for 5-15 minutes to obtain a first solution;

[0042] Step S200, adding 1 part of metal oxide and 25-60 parts of water to the first solution, stirring and heating for 4-6 hours at a heating temperature of 70-85° C. to obtain a second solution;

[0043] Step S300, the second solution is allowed to stand for 4-6 hours, and the upper clear liquid is taken as the electroplating additive solution.

[0044] In this embodiment, after the alkali metal hydroxide and the oleic acid ester are mixed and reacted, the reaction product will be complexed with the metal oxide, so that the metal oxide will not be precipitated in the electroplating mixture.

[0045] In a third aspect, an embodiment of the present invention further provides a hard silver graphene electroplating mixed solution, which comprises a silver salt, a complexing agent, graphene, a dispersant and the electroplating additive solution described above.

[0046] Silver salts include, but are not limited to, potassium silver cyanide.

[0047] Dispersants include, but are not limited to, one or more of aminosalicylate, polyparaben, and polyacrylate.

[0048] Alternatively, aminosalicylic acid salts include but are not limited to sodium aminosalicylic acid; polyacrylic acid salts include but are not limited to sodium polyacrylate.

[0049] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of silver salt is 40-60g / L, such as 45-55g / L, 48-52g / L, 40-45g / L, 55-60g / L, 42-49g / L, 51-59g / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0050] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of the complexing agent is 100-200 g / L, such as 130-170 g / L, 145-155 g / L, 100-130 g / L, 170-200 g / L, 120-150 g / L, 150-180 g / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0051] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of graphene is 1-3g / L, such as 1.5-2.5g / L, 1.7-2.3g / L, 1-1.5g / L, 2.5-3g / L, 1.2-1.8g / L, 2.2-2.9g / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0052] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of the dispersant is 0.5-3.9 g / L, such as 1.5-3 g / L, 1.8-2.4 g / L, 1-1.5 g / L, 3-3.9 g / L, 1.1-1.8 g / L, 2.4-3.6 g / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0053] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of the electroplating additive solution is 7-12 ml / L, such as 8-11 ml / L, 9-10 ml / L, 7-8 ml / L, 11-12 ml / L, 7-9 ml / L, 10-12 ml / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0054] Optionally, in the electroplating mixed solution of this embodiment, the dispersant includes sodium aminosalicylate, polyparahydroxybenzoate, and sodium polyacrylate. The concentration of sodium aminosalicylate is 0.1-1 g / L, for example, 0.3-0.7 g / L, 0.4-0.5 g / L, 0.1-0.3 g / L, 0.7-1 g / L, 0.3-0.5 g / L, 0.4-0.8 g / L, etc.; the concentration of polyparahydroxybenzoate is 0.1-2 g / L, for example, 0.6-1.4 g / L, 0.8-1.2 g / L. , 0.1-0.6g / L, 1.4-2g / L, 0.2-0.8g / L, 1.2-1.8g / L, etc.; the concentration of sodium polyacrylate is 0.3-0.9g / L, for example, 0.5-0.7g / L, 0.3-0.5g / L, 0.7-0.9g / L, 0.4-0.6g / L, 0.6-0.8g / L, 0.55-0.65g / L. Within the above concentration range, sodium aminosalicylate, polyparaben, and sodium polyacrylate can cooperate synergistically, which is conducive to obtaining an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refining the crystallization of the coating, and improving the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0055] The electroplating mixed solution of the present invention comprises a dispersant and the electroplating additive solution described above, wherein the electroplating additive solution comprises oleate and metal oxide. The metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. The alkali metal hydroxide can react with the oleate, and the product obtained by the reaction can be complexed with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixed solution, and then when the electroplating mixed solution is used to make a plated part, the metal oxide can be uniformly dispersed in the coating, thereby improving the hardness of the coating as a whole. The oleate can also lubricate the surface of graphene to prevent graphene from agglomerating. The oleate and the dispersant also have a synergistic effect, and the two cooperate to disperse graphene and metal oxide, which not only reduces the amount of the dispersant, but also makes each ion, metal oxide and graphene reach an ideal migration rate in the electroplating mixed solution, thereby facilitating the preparation of a coating with excellent thermal conductivity, electrical conductivity and hardness.

[0056] In a fourth aspect, an embodiment of the present invention further provides a plated component, wherein at least one surface of the plated component is combined with a plating layer, and the plating layer is prepared by electroplating or other methods using the hard silver graphene electroplating mixture described above.

[0057] The present invention will be specifically described below through specific examples. The following examples are only partial embodiments of the present invention and are not intended to limit the present invention.

[0058] Electroplating mixed solution embodiment 1

[0059] Preparation of electroplating additive solution:

[0060] Mix 4 parts of potassium hydroxide and 3 parts of trimethylolpropane oleate, and stir for 5-15 minutes to obtain a first solution;

[0061] Add 1 part of metal oxide and 45 parts of water to the first solution, stir and heat for 4-6 hours at a heating temperature of 70-85° C. to obtain a second solution;

[0062] The second solution is allowed to stand for 4-6 hours, and the upper clear liquid is taken as the electroplating additive solution.

[0063] Among them, 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0064] The hard silver graphene electroplating mixed solution is prepared by using the electroplating additive solution. The hard silver graphene electroplating mixed solution includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate.

[0065] Electroplating mixed solution embodiment 2

[0066] The electroplating mixed solution embodiment includes 7 ml / L of electroplating additive solution, 58 g / L of potassium silver cyanide, 120 g / L of potassium cyanide, 3 g / L of graphene, 0.3 g / L of sodium aminosalicylate, 1.5 g / L of polyparaben, and 0.4 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 5 parts of potassium hydroxide, 2 parts of trimethylolpropane oleate, and 30 parts of water, wherein 1 part of metal oxide includes 0.7 parts of antimony oxide, 0.2 parts of bismuth oxide, and 0.1 parts of manganese oxide.

[0067] Electroplating mixed solution embodiment 3

[0068] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide and 0.6 parts of manganese oxide, and does not contain bismuth oxide.

[0069] Electroplating mixed solution embodiment 4

[0070] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.5 parts of antimony oxide and 0.5 parts of bismuth oxide, and does not contain manganese oxide.

[0071] Electroplating mixed solution embodiment 5

[0072] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.8 parts of bismuth oxide and 0.2 parts of manganese oxide, and does not contain antimony oxide.

[0073] Electroplating mixed solution embodiment 6

[0074] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 1 part of antimony oxide, and does not contain bismuth oxide and manganese oxide.

[0075] Electroplating mixed solution embodiment 7

[0076] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 1 part of bismuth oxide, and does not contain antimony oxide and manganese oxide.

[0077] Electroplating mixed solution embodiment 8

[0078] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 1 part of manganese oxide, and does not contain antimony oxide and bismuth oxide.

[0079] Electroplating mixed solution embodiment 9

[0080] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 1 part of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0081] Electroplating mixed solution embodiment 10

[0082] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 4 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0083] Electroplating mixed solution embodiment 11

[0084] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 3 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0085] Electroplating mixed solution embodiment 12

[0086] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 6 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0087] Electroplating mixed solution embodiment 13

[0088] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 25 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0089] Electroplating mixed solution embodiment 14

[0090] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 60 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0091] Electroplating mixed solution embodiment 15

[0092] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.1 g / L of sodium aminosalicylate, 0.1 g / L of polyparaben, and 0.3 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0093] Electroplating mixed solution embodiment 16

[0094] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 1 g / L of sodium aminosalicylate, 2 g / L of polyparaben, and 0.9 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0095] Electroplating mixed solution comparative example 1

[0096] The present electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 4 parts of potassium hydroxide and 45 parts of water. The present electroplating mixed solution does not contain metal oxides and trimethylolpropane oleate.

[0097] Electroplating mixed solution comparative example 2

[0098] The electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 4 parts of potassium hydroxide, 3 parts of trimethylolpropane oleate, and 45 parts of water. The electroplating mixed solution does not contain metal oxides.

[0099] Electroplating mixed solution comparative example 3

[0100] The present electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 0.6 g / L of sodium aminosalicylate, 1 g / L of polyparaben, and 0.6 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide. The present electroplating mixed solution does not contain trimethylolpropane oleate.

[0101] Electroplating mixed solution comparative example 4

[0102] The present electroplating mixed solution embodiment includes 10 ml / L of electroplating additive solution, 50 g / L of potassium silver cyanide, 155 g / L of potassium cyanide, 2 g / L of graphene, 1.2 g / L of sodium aminosalicylate, 2.2 g / L of polyparaben, and 1.1 g / L of sodium polyacrylate; the electroplating additive solution includes 1 part of metal oxide, 4 parts of potassium hydroxide, and 45 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony oxide, 0.3 parts of bismuth oxide, and 0.3 parts of manganese oxide. The present electroplating mixed solution does not contain trimethylolpropane oleate.

[0103] Plated Example 1

[0104] At least one surface of the plated part of the present embodiment is provided with a plating layer, and the plating layer is obtained by electroplating the hard silver graphene electroplating mixed solution of the electroplating mixed solution embodiment 1 on the surface of the plated part.

[0105] Plated Parts Examples 2 to 16

[0106] Plated component embodiments 2 to 16 are substantially the same as plated component embodiment 1, except that the plating layers of plated component embodiments 2 to 16 use the hard silver graphene electroplating mixed solution of electroplating mixed solution embodiments 2 to 16.

[0107] Plated Comparative Examples 1 to 4

[0108] The plated comparative examples 1 to 4 are substantially the same as the plated example 1, except that the plated layers of the plated comparative examples 1 to 4 use the hard silver graphene electroplating mixed solution of the electroplating mixed solution comparative examples 1 to 4.

[0109] The coatings of the plated parts ...

[0110] Table 1:

[0111]

[0112] From Table 1 we can see that:

[0113] Compared with the average number of frictions that can be borne per micron of the coating of the plated comparative examples 1 to 4, the average number of frictions that can be borne per micron of the coating of the plated examples 1 to 16 is higher, and the wear resistance is increased by more than 10%. The reason is that the hard silver graphene electroplating mixture used in the preparation of the coating of the plated examples 1 to 16 includes the electroplating additive solution of the present invention, and the electroplating additive solution includes oleic acid ester and metal oxide. Metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the wear resistance of the coating finally formed. Alkali metal hydroxide can react with oleic acid ester, and the product obtained by the reaction will be complexed with metal oxide, so that the metal oxide will not precipitate in the electroplating mixture, and the metal oxide can be evenly dispersed in the coating, thereby improving the wear resistance of the coating.

[0114] Compared with the hardness of the coating of the plated comparative examples 1 to 4, the hardness of the coating of the plated examples 1 to 16 is higher, because the hard silver graphene electroplating mixture used in the preparation of the coating of the plated examples 1 to 16 includes the electroplating additive solution of the present invention, and the electroplating additive solution includes oleic acid ester and metal oxide. The metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. Alkali metal hydroxide can react with oleic acid ester, and the product obtained by the reaction will complex with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixture, and the metal oxide can be evenly dispersed in the coating, so that the coating has good hardness.

[0115] Compared with the plated comparative example 4, the plated layer of the plated example 1 has a higher hardness, a higher average number of frictions that the plated layer can withstand per micron, and a smaller amount of sodium aminosalicylate, polyparaben, and sodium polyacrylate is used. The reason is that the hard silver graphene electroplating mixed solution used in the preparation of the plated layer of the plated example 1 includes the electroplating additive solution of the present invention, and the electroplating additive solution includes oleate. Oleate and the dispersant have a synergistic effect, and the two cooperate to disperse graphene and metal oxides, which not only reduces the amount of dispersant used, but also enables each ion, metal oxide, and graphene to reach an ideal migration rate in the electroplating mixed solution, thereby facilitating the preparation of a plated layer with excellent thermal conductivity, electrical conductivity, and hardness.

[0116] The electroplating additives, electroplating additive solutions and preparation methods, and hard silver graphene electroplating mixed solutions provided in the embodiments of the present invention are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the methods of the present invention and its core ideas. At the same time, for those skilled in the art, according to the ideas of the present invention, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. An electroplating additive solution, characterized in that: The electroplating additives include metal oxides, oleic acid esters, alkali metal hydroxides, and water; The mass ratio of the metal oxide, oleate, alkali metal hydroxide and water is 1:(1-4):(3-6):(25-60).

2. The electroplating additive solution according to claim 1, characterized in that The metal oxide includes one or more of antimony oxide, bismuth oxide, and manganese oxide.

3. The electroplating additive solution according to claim 1, characterized in that The alkali metal hydroxide includes one or more of sodium hydroxide and potassium hydroxide.

4. The electroplating additive solution according to claim 1, characterized in that The oleic acid ester includes one or more of trimethylolpropane oleic acid ester, pentaerythritol oleic acid ester, isooctyl oleate, and neopentyl glycol dioleic acid ester.

5. A method for preparing the electroplating additive solution according to any one of claims 1 to 4, characterized in that: The method comprises: mixing an alkali metal hydroxide and an oleic acid ester, and stirring to obtain a first solution; adding a metal oxide and water to the first solution, stirring and heating to obtain a second solution; The second solution is allowed to stand, and the upper clear liquid is taken as the electroplating additive solution.

6. The method for preparing the electroplating additive solution according to claim 5, characterized in that: The stirring time of the first solution is 5-15 minutes; The heating time of the second solution is 4-6 hours, and the heating temperature is 70-85° C.; The second solution is allowed to stand for 4-6 hours.

7. A hard silver graphene electroplating mixed solution comprising the electroplating additive solution according to any one of claims 1 to 4, characterized in that: The electroplating mixed solution also includes silver salt, complexing agent, graphene and dispersant.

8. The hard silver graphene electroplating mixed solution according to claim 7, characterized in that: The silver salt comprises potassium silver cyanide; and / or The complexing agent includes one or more of potassium cyanide and sodium cyanide; and / or The dispersant includes one or more of aminosalicylic acid salt, polyparahydroxybenzoic acid ester and polyacrylic acid salt.

9. The hard silver graphene electroplating mixed solution according to claim 7, characterized in that: In the electroplating mixed solution, the concentration of the silver salt is 40-60 g / L; and / or In the electroplating mixed solution, the concentration of the complexing agent is 100-200 g / L; and / or In the electroplating mixed solution, the concentration of the graphene is 1-3 g / L; and / or In the electroplating mixed solution, the concentration of the dispersant is 0.5-3.9 g / L; and / or In the electroplating mixed solution, the concentration of the electroplating additive solution is 7-12 ml / L.

10. The hard silver graphene electroplating mixed solution according to claim 9, characterized in that: The dispersant includes sodium aminosalicylate with a concentration of 0.1-1 g / L, polyparaben with a concentration of 0.1-2 g / L, and sodium polyacrylate with a concentration of 0.3-0.9 g / L.

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