CN115182021A - Composite dispersant and mixed electroplating solution - Google Patents
Composite dispersant and mixed electroplating solution Download PDFInfo
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- CN115182021A CN115182021A CN202110358649.0A CN202110358649A CN115182021A CN 115182021 A CN115182021 A CN 115182021A CN 202110358649 A CN202110358649 A CN 202110358649A CN 115182021 A CN115182021 A CN 115182021A
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- sulfonic acid
- naphthol
- compound
- dispersant
- acid condensate
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 111
- 238000009713 electroplating Methods 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 62
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 41
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 27
- 239000012153 distilled water Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims description 75
- 239000004332 silver Substances 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 74
- 238000007747 plating Methods 0.000 claims description 64
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 47
- -1 formaldehyde sulfonic acid sodium salt Chemical class 0.000 claims description 46
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 45
- 159000000000 sodium salts Chemical class 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VVPHSMHEYVOVLH-UHFFFAOYSA-N 6-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(O)=CC=C21 VVPHSMHEYVOVLH-UHFFFAOYSA-N 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- MVEOHWRUBFWKJY-UHFFFAOYSA-N 7-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(O)=CC=C21 MVEOHWRUBFWKJY-UHFFFAOYSA-N 0.000 claims description 11
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 8
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 150000005215 alkyl ethers Chemical class 0.000 claims description 5
- 229920000417 polynaphthalene Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 37
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 23
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to the technical field of materials, in particular to two compound dispersants; the first compound dispersant consists of distilled water, naphthol sulfonic acid condensate salt and strong alkali; the second compound dispersant consists of the first compound dispersant and a nonionic surfactant, wherein the nonionic surfactant is a polyoxyethylene ether compound; the two compound dispersing agents can effectively block or slow down the agglomeration of graphene in the dispersing liquid. The invention also relates to a mixed electroplating solution containing the compound dispersing agent, wherein the graphene is uniformly and stably dispersed.
Description
Technical Field
The invention relates to the technical field of materials, in particular to two compound dispersing agents and a mixed electroplating solution containing the compound dispersing agents.
Background
Graphene is a two-dimensional crystal material and has excellent electrical, thermal and mechanical properties, wherein the thermal conductivity of single-layer graphene is as high as 5150W (m.K), and the carrier mobility reaches 15000cm < 2 > (V.S); compared with other reinforced phase composite electrical contact materials, the metal-based graphene composite electrical contact material has better electrical conductivity, wear resistance and thermal conductivity, and the graphene has good stability and does not have the problem of dielectric corrosion after the graphene is compounded with metal.
The graphene sheets have stronger pi-pi acting force, so that the single-layer graphene dispersed in the dispersion liquid is easy to agglomerate to form graphite again, and the performance of the graphene is seriously influenced; due to the special hydrophobic and oleophobic structure of graphene, the graphene can be stably dispersed in water or other solvents only by adding special surfactants and penetrants, so that the graphene is electroplated on the metal surface, and the metal-based graphene composite electrical contact material is obtained.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides two complex dispersing agents which can effectively block or slow the agglomeration of graphene in a dispersing solution; the mixed electroplating liquid is provided, and graphene is uniformly and stably dispersed.
In order to realize the purpose, the invention adopts the following technical scheme:
a compound dispersant is composed of distilled water, naphthol sulfonic acid condensate salt and strong alkali.
Preferably, the naphthol sulfonic acid condensate salt comprises one or more of a sodium salt of a 2-naphthol-6 sulfonic acid condensate, a sodium salt of a 2-naphthol-7 sulfonic acid condensate, a sodium salt of polynaphthalene formaldehyde sulfonic acid and a sodium salt of a 1-naphthol-4 sulfonic acid condensate.
Preferably, the strong base comprises one or more of potassium hydroxide and sodium hydroxide.
The compound dispersant consists of the compound dispersant and a nonionic surfactant, wherein the nonionic surfactant is a polyoxyethylene ether compound.
Preferably, the polyoxyethylene ether compound comprises one or more of polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonyl phenyl ether and polyoxyethylene polyoxypropylene alkylamine.
Preferably, the naphthol sulfonic acid condensate salt comprises one or more of a sodium salt of a 2-naphthol-6 sulfonic acid condensate, a sodium salt of a 2-naphthol-7 sulfonic acid condensate, a sodium salt of polynaphthalene formaldehyde sulfonic acid and a sodium salt of a 1-naphthol-4 sulfonic acid condensate.
Preferably, the strong base comprises one or more of potassium hydroxide and sodium hydroxide.
A mixed electroplating solution, which comprises the compound dispersant, a silver-based aqueous solution and graphene; the silver base aqueous solution includes KCN and silver ions.
Preferably, the mass volume concentration of KCN in the silver basic aqueous solution is 90.0-200.0g/L.
Preferably, the mass volume concentration of the silver ions in the silver basic aqueous solution is 15.0-50.0g/L.
Preferably, the mass volume concentration of the graphene in the mixed electroplating liquid is 1.0-20.0g/L.
Preferably, the volume ratio concentration of the compound dispersant in the mixed electroplating solution is 15.0-50.0ml/L.
Preferably, the mixed plating solution has a barrel plating current density of 0.5 to 0.7A/dm 2 。
Preferably, in the mixed electroplating solution, the rack plating current density is 0.7-1.0A/dm 2 。
According to the two compound dispersing agents, the components are synergistic, lipophilic groups in the dispersing agents can be adsorbed on the surfaces of graphene particles to form an enclosing layer, the agglomeration of graphene in a dispersing solution can be effectively blocked or slowed down, and in addition, hydrophilic groups in the dispersing agents are combined with OH-ions in water, so that the graphene is uniformly and stably dispersed in the dispersing solution.
According to the mixed electroplating solution, the complex dispersing agent can effectively block or slow down the agglomeration of graphene, and ensure that the graphene is uniformly and stably dispersed, so that the uniformity of the graphene dispersion in a graphene-silver mixed electroplating layer of an electroplating product is improved, and the product performance of the electroplating product is improved.
Detailed Description
The following examples are provided to further describe embodiments of the composite dispersant and the mixed plating solution of the present invention. The composite dispersant and the mixed plating solution of the present invention are not limited to the description of the following examples.
The invention discloses a compound dispersant, which is a first compound dispersant and consists of distilled water, naphthol sulfonic acid condensate salt and strong base.
The invention also discloses another compound dispersant which is a second compound dispersant and consists of the first compound dispersant and a nonionic surfactant, wherein the nonionic surfactant is a polyoxyethylene ether compound.
According to the two compound dispersing agents, the components are synergistic, lipophilic groups in the dispersing agents can be adsorbed on the surfaces of graphene particles to form an enclosing layer, the agglomeration of graphene in a dispersing solution can be effectively blocked or slowed down, and in addition, hydrophilic groups in the dispersing agents are combined with OH-ions in water, so that the graphene is uniformly and stably dispersed in the dispersing solution.
The invention discloses a mixed electroplating solution, which comprises a compound dispersant (a first compound dispersant or a second compound dispersant), a silver-based aqueous solution and graphene; the silver base aqueous solution includes KCN and silver ions.
According to the mixed electroplating liquid, the compound dispersing agent can effectively block or slow down the agglomeration of graphene, and ensure that the graphene is uniformly and stably dispersed, so that the uniformity of the dispersion of the graphene in a graphene-silver mixed electroplating layer of an electroplating product is improved, and the product performance of the electroplating product is improved.
The following examples will further illustrate the composite dispersant and the mixed plating solution of the present invention.
The following is an embodiment of the first composite dispersant of the present invention.
The first compound dispersant consists of distilled water, condensate of naphthol sulfonate and strong alkali.
Preferably, the naphthol sulfonic acid condensate salt comprises one or more of 2-naphthol-6 sulfonic acid condensate sodium salt, 2-naphthol-7 sulfonic acid condensate sodium salt, polynaphthalene formaldehyde sulfonic acid sodium salt and 1-naphthol-4 sulfonic acid condensate sodium salt.
Preferably, in the first composite dispersant, the mass fraction of the naphthol sulfonic acid condensate salt is 1 to 10%. Further, in the first composite dispersant, the mass fraction of the naphthol sulfonic acid condensate salt is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Preferably, the strong base comprises one or more of potassium hydroxide and sodium hydroxide.
Preferably, in the first compound dispersant, the mass fraction of the strong base is 1-10%. Further, in the first composite dispersant, the mass fraction of the strong base is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.
The following is an embodiment of the second composite dispersant of the present invention.
The second compound dispersant is composed of the first compound dispersant and a nonionic surfactant, wherein the nonionic surfactant is a polyoxyethylene ether compound.
Preferably, in the second composite dispersant, the mass fraction of the naphthol sulfonic acid condensate salt is 1 to 10%. Further, in the second composite dispersant, the mass fraction of the naphthol sulfonic acid condensate salt is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Preferably, the strong base comprises one or more of potassium hydroxide and sodium hydroxide.
Preferably, in the second compound dispersant, the mass fraction of the strong base is 1-10%. Further, in the second composite dispersant, the mass fraction of the strong base is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.
Preferably, the polyoxyethylene ether compound comprises one or more of polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonyl phenyl ether and polyoxyethylene polyoxypropylene alkylamine.
Preferably, the mass fraction of the polyoxyethylene ether compound in the second compound dispersant is 1-10%. Further, the second composite dispersant is a polyoxyethylene ether compound having a mass fraction of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
The invention also discloses a preparation method of the compound dispersant, which comprises the following operations: adding into distilled water with the temperature of T0, wherein T0 is more than or equal to 40 ℃ and less than or equal to 60 ℃; adding naphthol sulfonic acid condensate salt, strong base and optionally added nonionic surfactant, stirring for t0, t0 is more than or equal to 5min and less than or equal to 10min, supplementing distilled water, and stirring to obtain the compound dispersing agent. It should be noted that the term "optionally added nonionic surfactant" means that, in the preparation of the first complex dispersant, no nonionic surfactant is added; when the second compound dispersant is prepared, a nonionic surfactant is added.
Preferably, T0 is 50 ℃ and T0 is 10min.
Preferably, T0 is 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃.
Preferably, t0 is 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min.
Specifically, M kg of compound dispersant is prepared in advance, and the required distilled water mass is calculated; step 1, taking 75-95% (for example, 75%, 80%, 85%, 86%, 90%, 91% or 95%) of the required distilled water by mass, heating to a temperature T0, adding naphthol sulfonic acid condensate salt, strong base and optionally added nonionic surfactant, stirring for a time T0, supplementing distilled water, and stirring to obtain M kg of the compound dispersant.
The following are specific examples of the complex dispersant of the present invention.
Example 1:
the complex dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt and strong base, wherein the naphthol sulfonic acid condensate salt is 2-naphthol-7-sulfonic acid condensate sodium salt, and the strong base is potassium hydroxide; in the compound dispersing agent, the mass fraction of naphthol sulfonic acid condensate salt is 5%, the mass fraction of strong base is 4%, and the balance is distilled water.
Example 2:
the complex dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt, strong base and nonionic surfactant, wherein the naphthol sulfonic acid condensate salt is 2-naphthol-7-sulfonic acid condensate sodium salt, the strong base is potassium hydroxide, and the nonionic surfactant is polyoxyethylene lauryl ether; in the compound dispersing agent, the mass fraction of naphthol sulfonic acid condensate salt is 5%, the mass fraction of strong base is 4%, the mass fraction of nonionic surfactant is 4.5%, and the balance is distilled water.
Example 3:
the complex dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt and strong base, wherein the naphthol sulfonic acid condensate salt is 2-naphthol-6-sulfonic acid condensate sodium salt, and the strong base is potassium hydroxide; in the compound dispersing agent, the mass fraction of naphthol sulfonic acid condensate salt is 5%, the mass fraction of strong base is 4%, and the balance is distilled water.
Example 4:
the compound dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt, strong base and nonionic surfactant, wherein the naphthol sulfonic acid condensate salt is 2-naphthol-6-sulfonic acid condensate sodium salt, the strong base is potassium hydroxide, and the nonionic surfactant is polyoxyethylene lauryl ether; in the compound dispersing agent, the mass fraction of naphthol sulfonic acid condensate salt is 5%, the mass fraction of strong base is 4.5%, the mass fraction of nonionic surfactant is 4.5%, and the balance is distilled water.
Example 5:
the complex dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt and strong base, wherein the naphthol sulfonic acid condensate salt is 2-naphthol-7-sulfonic acid condensate sodium salt and 2-naphthol-6-sulfonic acid condensate sodium salt, and the strong base is potassium hydroxide and sodium hydroxide; in the compound dispersing agent, the mass fraction of naphthol sulfonic acid condensate salt is 10%, the mass fraction of strong base is 10%, and the balance is distilled water.
Preferably, in the compound dispersant of this example, the mass fraction of the sodium salt of the 2-naphthol-7-sulfonic acid condensate is 3%, and the mass fraction of the sodium salt of the 2-naphthol-6-sulfonic acid condensate is 7%.
Preferably, in the compound dispersant of the present example, the mass fraction of the strong potassium oxide is 5%, and the mass fraction of the sodium hydroxide is 5%.
Example 6:
the complex dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt and strong base, wherein the naphthol sulfonic acid condensate salt is 2-naphthol-6-sulfonic acid condensate sodium salt, and the strong base is potassium hydroxide; in the compound dispersant, the mass fraction of naphthol sulfonic acid condensate salt is 1%, the mass fraction of strong base is 1%, and the balance is distilled water.
Example 7:
the complex dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt, strong base and nonionic surfactant, wherein the naphthol sulfonic acid condensate salt is sodium salt of 2-naphthol-7-sulfonic acid condensate, sodium salt of 1-naphthol-4 sulfonic acid condensate and sodium salt of 2-naphthol-6 sulfonic acid condensate, the strong base is potassium hydroxide and sodium hydroxide, and the nonionic surfactant is polyoxyethylene lauryl ether, polyoxyethylene alkyl ether and polyoxyethylene nonyl phenyl ether; in the compound dispersing agent, the mass fraction of naphthol sulfonic acid condensate salt is 7%, the mass fraction of strong base is 7%, the mass fraction of nonionic surfactant is 8%, and the balance is distilled water.
Preferably, in the compound dispersant of the present embodiment, the mass fraction of the sodium salt of the 2-naphthol-7-sulfonic acid condensate is 3%, the mass fraction of the sodium salt of the 1-naphthol-4-sulfonic acid condensate is 2%, and the mass fraction of the sodium salt of the 2-naphthol-6-sulfonic acid condensate is 2%.
Preferably, in the compound dispersant of the present embodiment, the mass fraction of potassium hydroxide is 3% and the mass fraction of sodium hydroxide is 4%.
Preferably, in the composite dispersant of the present example, the mass fraction of polyoxyethylene lauryl ether is 3%, the mass fraction of polyoxyethylene alkyl ether is 3%, and the mass fraction of polyoxyethylene nonyl phenyl ether is 2%.
Example 8:
the compound dispersant of the embodiment comprises distilled water, naphthol sulfonic acid condensate salt, strong base and nonionic surfactant, wherein the naphthol sulfonic acid condensate salt is 2-naphthol-6-sulfonic acid condensate sodium salt, the strong base is potassium hydroxide, and the nonionic surfactant is polyoxyethylene lauryl ether; in the compound dispersing agent, the mass fraction of naphthol sulfonic acid condensate salt is 3%, the mass fraction of strong base is 3%, the mass fraction of nonionic surfactant is 3%, and the balance is distilled water.
One embodiment of the mixed plating solution of the present invention is described below.
The mixed electroplating solution comprises the compound dispersing agent, a silver basic aqueous solution and graphene, wherein the silver basic aqueous solution comprises KCN and silver ions.
Preferably, the mass volume concentration of KCN in the silver basic aqueous solution is 90.0-200.0g/L. Furthermore, the mass volume concentration of KCN in the silver basic aqueous solution is 90.0g/L, 100.0g/L, 110.0g/L, 120.0g/L, 130.0g/L, 140.0g/L, 150.0g/L, 160.0g/L, 170.0g/L, 180.0g/L, 190.0g/L or 200.0g/L.
Preferably, the mass volume concentration of the silver ions in the silver basic aqueous solution is 15.0-50.0g/L. Furthermore, the mass volume concentration of silver ions in the silver basic aqueous solution is 15.0g/L, 20.0g/L, 25.0g/L, 30.0g/L, 35.0g/L, 40.0g/L, 45.0g/L or 50.0g/L.
Preferably, the silver ions are provided from an aqueous solution produced by electrolysis of silver plates.
Preferably, in the mixed electroplating solution of the invention, the mass volume concentration of the graphene is 1.0-20.0g/L. Furthermore, in the mixed electroplating solution, the mass volume concentration of the graphene is 1.0g/L, 2.0g/L, 3.0g/L, 4.0g/L, 5.0g/L, 6.0g/L, 7.0g/L, 8.0g/L, 9.0g/L, 10.0g/L, 11.0g/L, 12.0g/L, 13.0g/L, 14.0g/L, 15.0g/L, 16.0g/L, 17.0g/L, 18.0g/L, 19.0g/L or 20.0g/L.
Preferably, the volume ratio concentration of the composite dispersant in the mixed electroplating solution of the present invention is 15.0 to 50.0ml/L. Furthermore, in the mixed plating solution of the invention, the volume ratio concentration of the compound dispersant is 15.0ml/L, 20.0ml/L, 25.0ml/L, 30.0 ml 1/L, 35.0ml/L, 40.0ml/L, 45.0ml/L or 50.0ml/L.
Preferably, the mixed electroplating solution of the invention has a barrel plating current density of 0.5-0.7A/dm 2 . Further, the mixed plating solution of the invention has a barrel plating current density of 0.5A/dm 2 、0.6A/dm 2 Or 0.7A/dm 2 。
Preferably, the rack plating current density of the mixed electroplating solution is 0.7-1.0A/dm 2 . Furthermore, the rack plating current density of the mixed electroplating solution is 0.7A/dm 2 、0.8A/dm 2 、0.9A/dm 2 Or 1.0A/dm 2 。
The following are specific examples of the mixed plating solution of the present invention.
Example 9:
the mixed electroplating solution comprises the compound dispersing agent, the silver basic aqueous solution and the graphene, wherein the compound dispersing agent, the silver basic aqueous solution and the graphene are obtained in example 1, and the silver basic aqueous solution comprises KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 30ml/L, and the mass volume concentration of graphene is 2.0g/L.
Preferably, the mixed plating solution of the present example has a barrel plating current density of 0.6A/dm 2 。
Preferably, the rack plating current density of the mixed plating solution of the present example is 0.8A/dm 2 。
Example 10:
the mixed plating solution of the embodiment comprises the compound dispersant of the embodiment 2, a silver basic aqueous solution and graphene, wherein the silver basic aqueous solution comprises KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 30ml/L, and the mass volume concentration of graphene is 2.0g/L.
Preferably, the mixed plating solution of the present example has a barrel plating current density of 0.6A/dm 2 。
Preferably, the rack plating current density of the mixed plating solution of the embodiment is 0.8A/dm 2 。
Example 11:
the mixed plating solution of the embodiment comprises the compound dispersant of the embodiment 3, a silver basic aqueous solution and graphene, wherein the silver basic aqueous solution comprises KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 30ml/L, and the mass volume concentration of graphene is 2.0g/L.
Preferably, the mixed plating solution of the present example has a barrel plating current density of 0.6A/dm 2 。
Preferably, the rack plating current density of the mixed plating solution of the embodiment is 0.8A/dm 2 。
Example 12:
the mixed electroplating solution comprises the compound dispersing agent, the silver basic aqueous solution and the graphene, wherein the compound dispersing agent, the silver basic aqueous solution and the graphene are obtained in example 4; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 30ml/L, and the mass volume concentration of graphene is 2.0g/L.
Preferably, the mixed plating solution of the present example has a barrel plating current density of 0.6A/dm 2 。
Preferably, the rack plating current density of the mixed plating solution of the present example is 0.8A/dm 2 。
Example 13:
the mixed electroplating solution comprises the compound dispersing agent, the silver basic aqueous solution and the graphene, wherein the compound dispersing agent, the silver basic aqueous solution and the graphene are prepared in example 5; in the silver basic aqueous solution, the mass volume concentration of KCN is 200.0g/L, and the mass volume concentration of silver ions is 50.0g/L; in the mixed electroplating liquid, the volume ratio concentration of the compound dispersant is 50ml/L, and the mass volume concentration of the graphene is 20.0g/L.
Preferably, the mixed plating solution of the present example has a barrel plating current density of 0.5A/dm 2 。
Preferably, the rack plating current density of the mixed plating solution of the present example is 0.7A/dm 2 。
Example 14:
the mixed electroplating solution of the embodiment comprises the compound dispersing agent of the embodiment 6, a silver basic aqueous solution and graphene, wherein the silver basic aqueous solution comprises KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 90.0g/L, and the mass volume concentration of silver ions is 15.0g/L; in the mixed electroplating liquid, the volume ratio concentration of the compound dispersing agent is 15ml/L, and the mass volume concentration of the graphene is 1.0g/L.
Preferably, the mixed plating solution of the present embodiment has a barrel plating current density of 0.7A/dm 2 。
Preferably, the rack plating current density of the mixed plating solution of the embodiment is 1.0A/dm 2 。
Example 15:
the mixed electroplating solution of the embodiment comprises the compound dispersing agent of the embodiment 6, a silver basic aqueous solution and graphene, wherein the silver basic aqueous solution comprises KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 170.0g/L, and the mass volume concentration of silver ions is 40.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 40ml/L, and the mass volume concentration of the graphene is 10.0g/L.
Preferably, the mixed plating solution of the present example has a barrel plating current density of 0.6A/dm 2 。
Preferably, this embodimentThe rack plating current density of the mixed electroplating solution is 0.9A/dm 2 。
Example 16:
the mixed electroplating solution of the embodiment comprises the compound dispersing agent of the embodiment 6, a silver basic aqueous solution and graphene, wherein the silver basic aqueous solution comprises KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 120.0g/L, and the mass volume concentration of silver ions is 20.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 20ml/L, and the mass volume concentration of the graphene is 5.0g/L.
Preferably, the mixed plating solution of the present example has a barrel plating current density of 0.6A/dm 2 。
Preferably, the rack plating current density of the mixed plating solution of the embodiment is 0.8A/dm 2 。
Blank electroplating solution:
the blank electroplating solution comprises silver basic aqueous solution and graphene, wherein the silver basic aqueous solution comprises KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L; in the mixed electroplating liquid, the mass volume concentration of the graphene is 2.0g/L.
Preferably, the plating blank has a barrel plating current density of 0.6A/dm 2 。
Preferably, the rack plating current density of the blank plating solution is 0.8A/dm 2 。
The invention also discloses an electroplating method, which is used for electroplating the graphene-silver mixed electroplated layer on the product to be electroplated, and comprises the following operations: cleaning a product to be electroplated, putting the cleaned product to be electroplated into a potassium cyanide solution for cyanide activation, carrying out pre-silver plating on the product to be electroplated after cyanide activation, putting the product to be electroplated after pre-silver plating into the mixed electroplating solution for electroplating, and washing the electroplated product for multiple times.
The first table shows the physical parameters of the mixed plating solution and the blank plating solution (without adding the composite dispersant of the present invention) of each example, and the experimental data of the plated product of the plating sheet and the blank plating solution of each example (the larger the absolute value of the zeta potential value is, the better the graphene particle dispersibility in the mixed plating solution is, the smaller the particle size detection sheet diameter value is, the better the graphene dispersibility in the mixed plating solution is, and the larger the wear resistance value is, the better the wear resistance of the plated product is):
table one:
note: the wear resistance is the average sustainable number per micrometer in units of counts/min.
The experimental data show that the mixed electroplating solution ensures that the graphene is stably and uniformly distributed in the mixed electroplating solution, and can remarkably improve the uniformity of the graphene distribution in the silver-graphene coating, so that the product performance (including electrical conductivity, thermal conductivity, wear resistance and the like) of the electroplating product is remarkably improved, and the wear resistance of the electroplating product is improved by more than 5 times.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments and it is not intended to limit the invention to the specific embodiments described. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.
Claims (10)
1. The compound dispersant is characterized by comprising distilled water, naphthol sulfonic acid condensate salt and strong base.
2. The built dispersant of claim 1, characterized in that: the naphthol sulfonic acid condensate salt comprises one or more of 2-naphthol-6 sulfonic acid condensate sodium salt, 2-naphthol-7 sulfonic acid condensate sodium salt, polynaphthalene formaldehyde sulfonic acid sodium salt and 1-naphthol-4 sulfonic acid condensate sodium salt.
3. The compound dispersant of claim 1, characterized in that: the strong base comprises one or more of potassium hydroxide and sodium hydroxide.
4. A composite dispersant comprising the composite dispersant according to claim 1 and a nonionic surfactant, wherein the nonionic surfactant is a polyoxyethylene ether compound.
5. The compound dispersant of claim 4, characterized in that: the polyoxyethylene ether compound comprises one or more of polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene nonyl phenyl ether and polyoxyethylene polyoxypropylene alkylamine.
6. The built dispersant of claim 4, characterized in that: the naphthol sulfonic acid condensate salt comprises one or more of 2-naphthol-6 sulfonic acid condensate sodium salt, 2-naphthol-7 sulfonic acid condensate sodium salt, polynaphthalene formaldehyde sulfonic acid sodium salt and 1-naphthol-4 sulfonic acid condensate sodium salt.
7. The compound dispersant of claim 4, characterized in that: the strong base comprises one or more of potassium hydroxide and sodium hydroxide.
8. A mixed plating solution, comprising the composite dispersant according to any one of claims 1 to 7, a silver-based aqueous solution, and graphene; the silver base aqueous solution includes KCN and silver ions.
9. The mixed plating solution as set forth in claim 8, wherein: in the silver basic aqueous solution, the mass volume concentration of KCN is 90.0-200.0g/L.
10. The mixed plating solution as set forth in claim 8, wherein: in the silver basic aqueous solution, the mass volume concentration of silver ions is 15.0-50.0g/L;
in the mixed electroplating liquid, the mass volume concentration of the graphene is 1.0-20.0g/L;
in the mixed electroplating liquid, the volume ratio concentration of the compound dispersant is 15.0-50.0ml/L;
the barrel plating current density of the mixed electroplating solution is 0.5-0.7A/dm 2 ；
In the mixed electroplating solution, the rack plating current density is 0.7-1.0A/dm 2 。
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