CN113215628A - Electroplating solution and application thereof - Google Patents

Electroplating solution and application thereof Download PDF

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CN113215628A
CN113215628A CN202110490015.0A CN202110490015A CN113215628A CN 113215628 A CN113215628 A CN 113215628A CN 202110490015 A CN202110490015 A CN 202110490015A CN 113215628 A CN113215628 A CN 113215628A
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plastic
solution
electroplating
deionized water
weight
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CN113215628B (en
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胡长昕
饶君豪
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Guangdong Yuhao New Material Technology Co ltd
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Guangdong Yuhao New Material Technology Co ltd
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    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The invention discloses an electroplating solution and application thereof, wherein the electroplating solution is prepared by mixing 1-3 wt% of copper sulfate, 1.5-5 wt% of sodium hypophosphite, 1-3 wt% of complexing agent, 0.1-1 wt% of accelerator, 0.1-1 wt% of stabilizer and the balance of water. The complexing agent, the stabilizing agent and the accelerator are added into the electroplating solution, so that the precipitation speed of copper ions in the electroplating process is effectively controlled, the occurrence of polarization phenomenon is reduced, and the uniformity and the stability of a plating layer are improved. The electroplating solution is used for electroplating the surface of the plastic, so that the wear resistance, the corrosion resistance and the binding force between the metal coating and the plastic are effectively improved.

Description

Electroplating solution and application thereof
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to electroplating solution and application thereof.
Background
Electroplating is a metal electrodeposition method for reducing metal ions in electroplating solution and depositing the metal ions on the surface of a material under direct current, and compared with surface treatment methods such as a vapor deposition mode and a coating, the method has the characteristics of uniform coating, moderate thickness, high speed and the like. The good electroplating solution can increase the stability and the oxidation resistance of the solution, improve the quality of a plating layer and enlarge the cathode current density range of metal. The plastic product has the advantages of easy processing, light weight, chemical stability and the like, and is widely applied to aspects of agriculture, industry, building, packaging and the like, but in some applications, the heat resistance, wear resistance and corrosion resistance of the plastic are still to be improved. The surface metallization of the plastic is an effective means, so that the advantages of the plastic, such as high rigidity, low density, high strength and easiness in processing, can be ensured, and the conductivity, wear resistance, magnetic conductivity, appearance and the like of the plastic can be improved. Generally, plastic is difficult to be completely soaked due to chemical inertness and hydrophobicity, so that the plastic is difficult to deposit on the surface of the plastic with metals such as silver, copper and the like, and a metal coating and the plastic are poor in adhesion, so that the phenomena of falling, bubbling and even plating leakage are easy to occur. Therefore, it is important to provide a plating solution and a method for plating a plastic surface that can solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides electroplating solution and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the first aspect of the invention provides a preparation method of electroplating solution, which comprises the steps of mixing 1-3 wt% of copper sulfate, 1.5-5 wt% of sodium hypophosphite, 1-3 wt% of complexing agent, 0.1-1 wt% of accelerator, 0.1-1 wt% of stabilizer and the balance of water, and then adjusting the pH value to 10-13 by using 1-4mol/L of sodium hydroxide.
The accelerator is any one of guanidine, glycine, benzotriazole, mercaptopyridine and mercaptopyrimidine; preferably, the accelerator is glycine.
The stabilizer is any one of 5, 5-diethyl hydantoin, thiourea derivatives, persulfate or thiosulfate; preferably, the stabilizer is 5,5 diethylhydantoin.
The complexing agent is chitosan or sulfhydryl chitosan.
The electroplating solution in the invention takes copper sulfate as a plating layer metal solution, sodium hypophosphite as a non-toxic and harmless reducing agent, a complexing agent for complexing copper ions, the speed of the electroplating process is effectively controlled, and a stabilizer for stabilizing the stability of the electroplating solution enables the electroplating solution to be uniform and stable, thereby improving the performance of the plating layer.
In the conventional electroless copper plating process, since the chemical equilibrium and the reduction potential value according to the chemical equilibrium are also changed by the polarization phenomenon generated at the time of deposition by the reduction reaction of copper ions, overvoltage is generated, and the mass transfer of copper ions is slow in the solution interior, and concentration polarization or a combination of both types of polarization phenomena occurs if the concentration deviation of the interface is increased. As a result, the rate of copper precipitation becomes very slow or even ceases, causing the coating to slow or cease to occur, ultimately resulting in non-uniformity and instability of the coating. Therefore, it is required to minimize the polarization phenomenon, which requires a proper control of the copper precipitation rate, an inhibition of electron movement or mass transfer by the addition of an accelerator or a copper complex ion salt, and a significant decrease in the concentration of free copper ions present in the plating solution after the addition of a complexing agent, which can effectively control the rapid-acting of the plating layer, and the kind and concentration of the complexing agent have a great influence on the copper precipitation rate.
Although chitosan has stronger complexing and adsorbing capacity, good mechanical property, high fixing efficiency and stable chemical property, the adhesion and the complexing property are further enhanced after the chitosan molecules are connected with sulfydryl, the chitosan can be effectively adsorbed on the surface of an electrode, and the sulfydryl chitosan has the characteristics of good stability and longer service life. The sulfhydryl group is easy to oxidize to form a disulfide bond, thereby forming a network structure and having obvious adsorption effect. The introduction of sulfhydryl groups imparts new biological properties to chitosan: when the content of sulfydryl is increased, the contact time between the mucous membrane and the thiolated chitosan is prolonged, and when the pH value is increased, the activity of sulfydryl is enhanced, and a plurality of disulfide bonds are formed inside the thiolated chitosan molecules.
According to the invention, the sulfydryl chitosan is obtained by reacting chitosan with sulfydryl polyethyleneimine or N-acetyl-L-cysteine, has a network structure, ensures the stability of plating solution, and can form a copper plating layer with hardness and flexibility required by the plating layer; in addition, a higher plating layer formation speed can be provided, and even if the number of times of use of the plating solution is increased, the utilization rate of the substance is improved, and the plating layer has excellent corrosion resistance and wear resistance.
Preferably, the complexing agent is sulfhydryl chitosan; the preparation method of the mercapto chitosan comprises the following steps:
mixing 0.5-3 parts by weight of chitosan, 0.5-1.5 parts by weight of N-hydroxysuccinimide and 50-100 parts by weight of water, stirring at the room temperature of 500rpm for 1-5min under 300-2 ℃, adding 1-6 parts by weight of sulfhydryl compound, adjusting the pH value of the reaction solution to 4-6 by using 0.5-2mol/L NaOH, reacting for 1-3h under the stirring at the temperature of 800rpm under 500-50 ℃, adding 50-80 parts by weight of absolute ethyl alcohol, standing for 1-3h, performing suction filtration, washing for 2-5 times by using the absolute ethyl alcohol, performing vacuum drying at the temperature of 40-70 ℃ for 6-12h, and refrigerating and storing at the temperature of 0-8 ℃ to obtain the sulfhydryl chitosan.
The sulfhydryl compound is sulfhydrylation polyethyleneimine and/or N-acetyl-L-cysteine; preferably, the mercapto compound is a mercapto polyethyleneimine and N-acetyl-L-cysteine in a mass ratio of 1: (1-5) in the presence of a catalyst.
The preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 0.5-2 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 1-4 parts by weight of methyl thioglycolate for mixing, stirring at 50-70 ℃ and 300-500rpm for 6-10h to obtain a mixed solution A, carrying out reduced pressure concentration at the vacuum degree of 0.06-0.09MPa and the temperature of 40-60 ℃ until 1/5-1/3 of the mixed solution A, adding 2-10 parts by weight of deionized water for dissolving, adding 2-8 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at the vacuum degree of 0.05-0.1MPa and the temperature of 40-60 ℃ until 1/5-1/3 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine.
An electroplating solution is prepared by adopting the method.
In a second aspect, the present invention provides the use of the above-mentioned electroplating solution for electroplating plastic surfaces.
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the surface of the plastic for 5-10min at room temperature by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1 (1-2); cleaning with 40-60 deg.C sodium carbonate water solution with pH of 7-8.5 for 3-10min, ultrasonic cleaning with acetic acid with pH of 5-6.5 at room temperature for 1-3min, and cleaning with 30-50 deg.C water for 2-5min to obtain pretreated plastic;
s2, coarsening: soaking the pretreated plastic in swelling solution at 30-50 deg.C for 5-15min, and then in microetching solution at 50-65 deg.C, and treating at ultrasonic frequency of 20-40kHz and ultrasonic power of 120-;
s3, neutralization: immersing the microetching plastic into a neutralization solution, stirring for 5-15min at 50-70 ℃ and 200-500rpm, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, 15-50 wt% of sulfuric acid and 1-5 wt% of oxalic acid are taken out and washed for 2-5min by deionized water;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 20-40min at 30-50 ℃, wherein the sensitizing solution is prepared by mixing 0.01-0.1 wt% of palladium chloride, 1-5 wt% of stannous chloride, 30-40 wt% of hydrochloric acid with the concentration of 20-40ml/L, 10-25 wt% of potassium chloride and the balance of deionized water;
s5, activation: placing the sensitized plastic in an activating solution, and activating at the room temperature and at the speed of 300-500rpm for 3-10min, wherein the activating solution is formed by mixing 1-5 wt% of silver nitrate, 0.5-2 wt% of ammonia water, 2-10 wt% of glyoxal, 0.5-3 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 20-30 ℃, and the current density is 0.5-2.0A/dm2Electroplating for 20-50 min;
s7, finished product: drying the electroplated plastic at 50-70 deg.C for 1-3h, and cooling to room temperature to obtain the plastic surface metal coating. The thickness of the metal plating layer is 0.2-10 μm.
The plastic is any one of polycarbonate plastic, ABS plastic and polyimide plastic.
The plastic surface shows obvious chemical inertness and hydrophobicity, is difficult to be completely soaked with aqueous solution, is difficult to form chemically bonded active functional groups with metals such as silver, copper, nickel and the like, and is difficult to induce the deposition of the metals. According to the invention, a specific swelling solution is firstly adopted for treatment in the roughening preparation process of the metal coating, so that on one hand, a swelling agent penetrates through the surface of the polymer to form a porous channel capable of penetrating into the polymer, thus the contact surface area between the substrate and the microetching agent is increased, and the oxidation-reduction reaction rate in the microetching process is increased; on the other hand, hydrophilic polar groups such as-COOH, -OH, -CHO and the like are formed on the surface of the plastic after the swelling treatment, so that reaction points on the surface of the substrate are fully exposed, and the two factors can obviously enhance the bonding strength between the substrate and the chemical plating layer.
The swelling solution is prepared by mixing 10-25 wt% of 5-carboxyl benzotriazole, 20-40 wt% of N-methyl pyrrolidone, 10-20 wt% of potassium hydroxide, 5-15 wt% of N, N-dimethylformamide and the balance of deionized water.
The micro-scaleThe etching solution comprises 20-30 wt% of phosphoric acid, 50-65 wt% of sulfuric acid and 3-8 wt% of MnO20.01 to 0.05 weight percent of hexadecyl trimethyl ammonium bromide, 0.1 to 1 weight percent of sodium tripolyphosphate and the balance of deionized water.
The invention has the beneficial effects that: the complexing agent, the stabilizing agent and the accelerator are added into the electroplating solution, so that the precipitation speed of copper ions in the electroplating process is effectively controlled, the occurrence of polarization phenomenon is reduced, and the uniformity and the stability of a plating layer are improved. The plastic surface electroplating method provided by the invention can effectively improve the wear resistance and the corrosion resistance, the bonding property between the metal coating and the plastic is strong, and the service life is prolonged.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
in the examples, the polycarbonate plastics are purchased from Yongde metallocene science and technology Limited of Shenzhen.
Examples cetyltrimethylammonium bromide, CAS: 57-09-0.
Examples sodium tripolyphosphate, CAS: 7758-29-4.
Examples oxalic acid, CAS: 144-62-7.
Examples palladium chloride, CAS: 7647-10-1.
Examples stannous chloride, CAS: 7772-99-8.
Examples glyoxal, CAS: 107-22-2.
Examples triethanolamine, CAS: 102-71-6.
Example 1, 2-cyclohexanediaminetetraacetic acid, CAS: 13291-61-7.
Copper sulfate, CAS: 7758-98-7.
Examples sodium hypophosphite, CAS: 7681-53-0.
MnO in examples2，CAS：1313-13-9。
Example 5,5 diethylhydantoin, CAS: 5455-34-5.
Example 4-mercaptopyridine, CAS: 4556-23-4.
Examples sodium persulfate, CAS: 7775-27-1.
Example 5-Carboxybenzotriazole, CAS: 23814-12-2.
Examples N-methylpyrrolidone, CAS: 872-50-4.
Examples N, N-dimethylformamide, CAS: 68-12-2.
In the examples, chitosan was purchased from wuhan woxuan science ltd, CAS: 9012-76-4, and the content of active substances is as follows: 99%, molecular weight: 3000 g/mol.
Examples N-hydroxysuccinimide, CAS: 6066-82-6.
Examples N-acetyl-L-cysteine, CAS: 616-91-1.
In the examples, polyethyleneimine is available from pharmaceutical chemicals, Inc. of Wuhan La Na white, CAS: 26658-46-8, molecular weight: 10000 g/mol.
Examples ethyl thioglycolate, CAS: 623-51-8.
Example 1
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: putting the pretreated plastic into microetching liquid with the ultrasonic power of 160W and the ultrasonic frequency of 25kHz at 55 ℃ for treating for 20min to obtain microetching plastic; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, washing with deionized water for 3 times;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid with the concentration of 30ml/L, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is 4-mercaptopyridine; the stabilizer is sodium persulfate; the complexing agent is chitosan.
Example 2
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling liquid is 20wt% 5-carboxyl benzotriazole, 30 wt% N-methyl pyrrolidone, 15 wt% potassium hydroxide, 10 wt% N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, washing with deionized water for 3 times;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid with the concentration of 30ml/L, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is 4-mercaptopyridine; the stabilizer is sodium persulfate; the complexing agent is chitosan.
Example 3
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is sodium persulfate; the complexing agent is chitosan.
Example 4
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is chitosan.
Example 5
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of glycine, 0.2 wt% of 5,5 diethyl hydantoin and the balance of deionized water, and adjusting the pH value to 11 by using 2mol/L of sodium hydroxide;
the electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is sulfhydryl chitosan.
The preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 30-50 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, carrying out suction filtration, washing for 3 times by using the absolute ethyl alcohol, carrying out vacuum drying at 50 ℃ for 10h, and carrying out cold storage at 4 ℃ to obtain the sulfhydryl chitosan; the sulfhydryl compound is N-acetyl-L-cysteine.
Example 6
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is sulfhydryl chitosan.
The preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 30-50 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, carrying out suction filtration, washing for 3 times by using the absolute ethyl alcohol, carrying out vacuum drying at 50 ℃ for 10h, and carrying out cold storage at 4 ℃ to obtain the sulfhydryl chitosan;
the mercapto compound is mercapto polyethyleneimine;
the preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 1.5 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 2 parts by weight of methyl thioglycolate, mixing, stirring at 60 ℃ and 400rpm for 8 hours to obtain a mixed solution A, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution A, adding 3 parts by weight of deionized water for dissolution, adding 5 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine.
Example 7
The plastic surface electroplating method comprises the following steps:
s1, preprocessing: firstly, cleaning the plastic for 8min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 7.5 at 50 deg.C for 5 min; cleaning with acetic acid water solution with pH of 6 for 2min, and cleaning with deionized water at 40 deg.C for 4min to obtain pretreated plastic; the plastic is polycarbonate plastic;
s2, coarsening: soaking the pretreated plastic in 40 ℃ swelling liquid for 10min, then placing the pretreated plastic in 55 ℃ microetching liquid, and treating the pretreated plastic for 20min under the ultrasonic power of 160W and the ultrasonic frequency of 25kHz to obtain microetching plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the microetching plastic into a neutralization solution, and stirring at 60 ℃ and 400rpm for 10min, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized plastic into a sensitizing solution, and soaking for 30min at 40 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized plastic in an activating solution, and activating at room temperature and 400rpm for 8min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 25 ℃, and the current density is 1A/dm2Electroplating time is 40 min;
s7, finished product: drying the electroplated plastic at 60 ℃ for 2h, and cooling to room temperature to obtain the plastic surface metal coating.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin;
the complexing agent is sulfhydryl chitosan; the preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 40 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, performing suction filtration, washing for 3 times by using the absolute ethyl alcohol, performing vacuum drying at 50 ℃ for 10h, and performing cold storage at 4 ℃ to obtain sulfhydryl chitosan;
the mercapto compound is a mixture of mercapto polyethyleneimine and N-acetyl-L-cysteine according to a mass ratio of 1: 2;
the preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 1.5 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 2 parts by weight of methyl thioglycolate, mixing, stirring at 60 ℃ and 400rpm for 8 hours to obtain a mixed solution A, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution A, adding 3 parts by weight of deionized water for dissolution, adding 5 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine.
Example 8
The preparation method of the wear-resistant ABS plastic comprises the following steps:
s1, preprocessing: firstly, cleaning ABS plastic for 10min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 8.5 at 60 deg.C for 10 min; cleaning with acetic acid water solution with pH of 6.5 for 3min, and cleaning with deionized water at 50 deg.C for 5min to obtain pretreated ABS plastic;
s2, coarsening: soaking the pretreated ABS plastic in swelling solution at 50 ℃ for 15min, then placing the soaked ABS plastic in microetching solution at 65 ℃ for 25min under the ultrasonic power of 200W and the ultrasonic frequency of 40kHz to obtain the microetching ABS plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl groupTrimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the micro-etched ABS plastic into a neutralization solution, and stirring for 15min at 70 ℃ and 500rpm, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized ABS plastic into a sensitizing solution, and soaking for 40min at 50 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized ABS plastic in an activating solution, and activating at room temperature and 500rpm for 10min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated ABS plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 30 ℃, and the current density is 2.0A/dm2Electroplating time is 50 min;
s7, finished product: drying the electroplated ABS plastic at 70 ℃ for 3h, and cooling to room temperature to obtain the wear-resistant ABS plastic.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin; the complexing agent is chitosan. The method of test example 2 is adopted to test the wear resistance of the wear-resistant ABS plastic of example 8, and the specific steps are as follows: the plastic surface was rubbed using a 7-IBB RCA abrader manufactured by nomen instruments, usa under 175 grams of force, and when the plastic matrix material was exposed, the number of revolutions of the rubber wheel was recorded, tested in parallel for 5 times, and averaged. Example 8 abrasion resistant ABS plastic has abrasion resistance 3510 cycles.
Example 9
The preparation method of the wear-resistant ABS plastic comprises the following steps:
s1, preprocessing: firstly, cleaning ABS plastic for 10min by using a mixture of acetone and absolute ethyl alcohol, wherein the mass ratio of the acetone to the absolute ethyl alcohol is 1: 1; cleaning with sodium carbonate water solution with pH of 8.5 at 60 deg.C for 10 min; cleaning with acetic acid water solution with pH of 6.5 for 3min, and cleaning with deionized water at 50 deg.C for 5min to obtain pretreated ABS plastic;
s2, coarsening: soaking the pretreated ABS plastic in swelling solution at 50 ℃ for 15min, then placing the soaked ABS plastic in microetching solution at 65 ℃ for 25min under the ultrasonic power of 200W and the ultrasonic frequency of 40kHz to obtain the microetching ABS plastic; the swelling solution is prepared by mixing 20 wt% of 5-carboxyl benzotriazole, 30 wt% of N-methyl pyrrolidone, 15 wt% of potassium hydroxide, 10 wt% of N, N-dimethylformamide and the balance of deionized water; the micro-etching solution consists of 25 wt% of phosphoric acid, 60 wt% of sulfuric acid and 5 wt% of MnO20.03 wt% of hexadecyl trimethyl ammonium bromide, 0.5 wt% of sodium tripolyphosphate and the balance of deionized water;
s3, neutralization: immersing the micro-etched ABS plastic into a neutralization solution, and stirring for 15min at 70 ℃ and 500rpm, wherein the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, the sulfuric acid accounts for 30 wt%, and the oxalic acid accounts for 3 wt%; taking out, and washing with deionized water for 5 min;
s4, sensitization: putting the neutralized ABS plastic into a sensitizing solution, and soaking for 40min at 50 ℃, wherein the sensitizing solution is prepared by mixing 0.015 wt% of palladium chloride, 2 wt% of stannous chloride, 37 wt% of hydrochloric acid, 15 wt% of potassium chloride and the balance of deionized water;
s5, activation: putting the sensitized ABS plastic in an activating solution, and activating at room temperature and 500rpm for 10min, wherein the activating solution is prepared by mixing 2 wt% of silver nitrate, 1.2 wt% of ammonia water, 5 wt% of glyoxal, 1.5 wt% of triethanolamine and the balance of deionized water;
s6, electroplating: the activated ABS plastic is put into electroplating solution for electroplating treatment, the electroplating temperature is 30 ℃, and the current density is 2A/dm2Electroplating time is 50 min;
s7, finished product: drying the electroplated ABS plastic at 70 ℃ for 3h, and cooling to room temperature to obtain the wear-resistant ABS plastic.
The electroplating solution is formed by mixing 1.8 wt% of copper sulfate, 2.4 wt% of sodium hypophosphite, 1.5 wt% of complexing agent, 0.4 wt% of accelerator, 0.2 wt% of stabilizer and the balance of deionized water, and the pH value is adjusted to 11 by using 2mol/L of sodium hydroxide;
the accelerator is glycine; the stabilizer is 5, 5-diethylhydantoin;
the complexing agent is sulfhydryl chitosan; the preparation method of the mercapto chitosan comprises the following steps: mixing 1 part by weight of chitosan, 0.8 part by weight of N-hydroxysuccinimide and 60 parts by weight of deionized water, stirring at room temperature of 400rpm for 3min, adding 3 parts by weight of sulfhydryl compound, adjusting the pH of a reaction solution to 5 by using 1mol/L NaOH, stirring at 600rpm and 40 ℃ for reaction for 2h, adding 60 parts by weight of absolute ethyl alcohol, standing for 2h, performing suction filtration, washing for 3 times by using the absolute ethyl alcohol, performing vacuum drying at 50 ℃ for 10h, and performing cold storage at 4 ℃ to obtain sulfhydryl chitosan;
the mercapto compound is a mixture of mercapto polyethyleneimine and N-acetyl-L-cysteine according to a mass ratio of 1: 2;
the preparation method of the sulfhydrylation polyethyleneimine comprises the following steps: dissolving 1.5 parts by weight of polyethyleneimine in absolute ethyl alcohol, adding 2 parts by weight of methyl thioglycolate, mixing, stirring at 60 ℃ and 400rpm for 8 hours to obtain a mixed solution A, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution A, adding 3 parts by weight of deionized water for dissolution, adding 5 parts by weight of ethyl acetate to obtain a mixed solution B, carrying out reduced pressure concentration at 0.08MPa vacuum degree and 50 ℃ to 1/4 of the mixed solution B, and carrying out freeze drying to obtain the sulfhydrylation polyethyleneimine. The wear resistance test of the wear-resistant ABS plastic of example 9 by the method of test example 2 comprises the following steps: the plastic surface was rubbed using a 7-IBB RCA abrader manufactured by nomen instruments, usa under 175 grams of force, and when the plastic matrix material was exposed, the number of revolutions of the rubber wheel was recorded, tested in parallel for 5 times, and averaged. Example 9 the abrasion resistant ABS plastic had 4652 cycles of abrasion resistance.
Test example 1
Coating bonding strength: taking the sectional area (S) as 1cm2Copper cylinder (D) and plastic sheets prepared in examples 1 to 7And (3) bonding the surface metal coating by using an adhesive, performing pressure curing at room temperature for 24h, removing the adhesive around the copper column by using a knife, and cutting the coating around the copper column (to a plastic substrate) to obtain a sample. The sample is arranged on a tensile machine, a pull-off experiment is carried out by using a force vertical to the surface of a plated part until a metal plating layer is separated from a plastic substrate, a tensile value (N) is recorded, and the peel strength Fr can be obtained by calculating according to the following formula:
FH＝N/S；
Fr＝FH·σ3/4/5.5；
wherein, FHThe pull-off strength (N/cm) of the plastic coating2) Fr is the peel strength (N/cm) of the plastic plating layer, and σ is the thickness (cm) of the metal layer to be peeled;
bonding strength of a hot stamping circulating plating layer at-55 ℃ to +125 ℃: the plastic surface metal-plated parts described in examples 1 to 7 were sequentially subjected to standing at-55 deg.C for 60 minutes, at 25 deg.C for 60 minutes, at 125 deg.C for 60 minutes, and at 25 deg.C for 60 minutes, to complete 1 cycle of warm punching at-55 deg.C to +125 deg.C. After 5-55 to +125 ℃ warm punching cycles are carried out on the plastic surface metal coating piece, whether bubbles, peeling, layering or other visible deformation and damage appear on the metal coating layer of the plastic surface metal coating piece is observed, and if no visible deformation and damage appear, a coating bonding strength test is carried out on the plastic piece subjected to the 5-55 to 125 ℃ warm punching cycles.
TABLE 1 test results of coating bonding strength of plastic surface metal-coated parts
Figure BDA0003051567210000171
The above results show that the swelling treatment and then the microetching treatment are carried out in the roughening process, which can effectively improve the bonding strength between the plastic and the metal coating, and the specific comparison example 1-2 shows that the swelling treatment and then the microetching treatment are carried out in the roughening process, which has better effect because the swelling agent can penetrate through the surface of the polymer to form a porous channel which can penetrate into the polymer, increase the contact surface area between the plastic and the microetching agent, and form a microscopic rugged appearance on the surface of the substrate through the redox effect in the microetching process, so that the appearance not only can increase the contact area between the surface of the substrate and the coating, but also can enable the coating to deposit on the surface of the substrate to generate an anchor effect, and simultaneously, when the plastic surface is formed, hydrophilic polar groups such as-COOH, -CHO, -OH and the like can be formed on the surface of the substrate, the adhesive force between the plastic surface and the chemical plating layer is improved; compared with the examples 4-5, the mercapto chitosan is added into the electroplating solution as a complexing agent, so that the bonding performance of the plating layer can be improved, and the adhesion and the complexing performance are further enhanced after the mercapto is grafted on the chitosan molecules, so that the mercapto chitosan can be effectively adsorbed on the surface of an electrode and easily oxidized to form a disulfide bond, thereby forming a network structure and having a remarkable adsorption effect;
compared with examples 5-7, the compound of sulfhydrylation polyethyleneimine and N-acetyl-L-cysteine is added in example 7 to modify chitosan, and the complexation strength of sulfhydryl in the N-acetyl-L-cysteine and chitosan is very high, and the adsorbability is very strong; the complexing strength of the sulfhydrylation polyethyleneimine and the chitosan is not as strong as that of sulfhydrylation and the chitosan in the N-acetyl-L-cysteine, but the sulfhydrylation polyethyleneimine can play a role of a surfactant and effectively stabilize the stability of the electroplating solution, so that the sulfhydrylation polyethyleneimine can be uniformly adsorbed on an electrode in the electroplating process, and the sulfhydrylation polyethyleneimine and the electrode are synergistic, so that the binding force between metal and plastic is enhanced, and the service life is prolonged.
Test example 2
And (3) testing the wear resistance: the plastic surface metal coatings of examples 1-7 were rubbed using a 7-IBB RCA abrader from Noman instruments and Equipment, USA, under 175 grams of force, and when the electroplated product was exposed to the plastic substrate, the number of rubber wheel revolutions was recorded and was found to be acceptable, and the test was performed 5 times in parallel, and the average was taken.
TABLE 2 abrasion resistance test results
Figure BDA0003051567210000181
Figure BDA0003051567210000191
Compared with the embodiment 1-2, before electroplating, swelling treatment is firstly carried out and then micro-etching is carried out in the roughening process, so that the thickness of the plating layer can be effectively improved, the swelling agent can penetrate through the surface of the polymer to form a porous channel capable of penetrating into the polymer, the contact surface area between the plastic and the micro-etching agent is increased, the roughness of the surface of the plastic is increased, and meanwhile, when the roughening is formed on the surface of the plastic, hydrophilic polar groups such as-COOH, -CHO, -OH and the like are formed on the surface of the substrate, so that the binding force between the surface of the plastic and the chemical plating layer is improved, the thickness of the plating layer is increased, and the wear resistance is further improved; comparing examples 2-4, in example 4, glycine is added as an accelerator and 5, 5-diethylhydantoin is added as a stabilizer, so that the thickness of the plating layer can be increased within the same time, the accelerator is added, the polarization phenomenon can be reduced to the maximum extent, the generation of overvoltage is reduced, the mass transfer of copper ions is promoted, the uniformity and the thickness of the plating layer are improved, and the wear resistance is improved; in comparative examples 4 to 7, the concentration of free copper ions present in the plating solution after the complexing agent is added is reduced, and the rapid action of the plating layer can be effectively controlled, while the addition of the stabilizing agent reduces the surface tension of the plating solution, inhibits the precipitation of copper on the inactive surface, improves the utilization rate of the substance and the efficiency of the plating layer, and further improves the wear resistance.
Test example 3
Salt spray test: the plastic surface metal coatings of examples 1-7 were placed in a salt spray box, the plastic surface metal coatings were sprayed with 5 wt% sodium chloride brine at 35 ℃, the surface of the coatings was observed, the time taken for the appearance of white spots or rust on the surface of the plated products was recorded, and the test was conducted 5 times in parallel, and the average value was taken, if the time was more than 48 hours, the pass was determined.
TABLE 3 salt spray test results
Figure BDA0003051567210000192
Figure BDA0003051567210000201
From the above results, it can be seen that the addition of the accelerator and the stabilizer to the electroplating solution can improve the salt spray resistance of the metal coating on the plastic surface to some extent, and the possible reason is that the electroplating solution is more stable in the presence of the accelerator and the stabilizer, so that the coating can be uniformly electroplated on the plastic shell, and the salt spray resistance can be further improved; the addition of the complexing agent can obviously improve the salt spray resistance of the metal coating on the surface of the plastic, and the reason is that the copper ion binding property of the mercapto chitosan complex is stronger, a part of mercapto chitosan is adsorbed on an electroplated layer, and the mercapto chitosan has the sodium chloride corrosion resistance, so that the salt spray resistance of the metal coating on the surface of the whole plastic is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1.一种电镀液的制备方法，其特征在于，包括以下步骤：将1-3wt％硫酸铜、1.5-5wt％次亚磷酸钠、1-3wt％络合剂、0.1-1wt％加速剂、0.1-1wt％稳定剂、余量为水混合，再用1-4mol/L氢氧化钠调节pH＝10-13，即得。1. a preparation method of electroplating solution, is characterized in that, comprises the following steps: 1-3wt% copper sulfate, 1.5-5wt% sodium hypophosphite, 1-3wt% complexing agent, 0.1-1wt% accelerator, Mix 0.1-1wt% stabilizer and the balance with water, and then adjust pH=10-13 with 1-4mol/L sodium hydroxide. 2.如权利要求1所述电镀液的制备方法，其特征在于，所述加速剂为胍、甘氨酸、苯并三唑、巯基吡啶、巯基嘧啶中的任一种；所述稳定剂为5,5二乙基海因、硫脲、硫脲衍生物、过硫酸盐或硫代硫酸盐中的任意一种。2. the preparation method of electroplating solution as claimed in claim 1, is characterized in that, described accelerator is any in guanidine, glycine, benzotriazole, mercaptopyridine, mercaptopyrimidine; Described stabilizer is 5, 5 Any one of diethyl hydantoin, thiourea, thiourea derivatives, persulfate or thiosulfate. 3.如权利要求1所述电镀液的制备方法，其特征在于，所述络合剂为壳聚糖或巯基壳聚糖；所述巯基壳聚糖的制备方法如下：3. the preparation method of electroplating solution as claimed in claim 1 is characterized in that, described complexing agent is chitosan or thiol chitosan; The preparation method of described thiol chitosan is as follows: 将0.5-3重量份壳聚糖、0.5-1.5重量份N-羟基琥珀酰亚胺、50-100重量份水混合，在300-500rpm下室温搅拌1-5min后，加入1-6重量份巯基化合物，用0.5-2mol/LNaOH将反应液pH调至4-6，在500-800rpm、30-50℃搅拌下反应1-3h，用加入50-80重量份无水乙醇，静置1-3h，抽滤，再用无水乙醇洗涤2-5次，40-70℃真空干燥6-12h，0-8℃下冷藏保存，得到巯基壳聚糖。Mix 0.5-3 parts by weight of chitosan, 0.5-1.5 parts by weight of N-hydroxysuccinimide, and 50-100 parts by weight of water, stir at room temperature for 1-5 minutes at 300-500 rpm, and add 1-6 parts by weight of mercapto compound, adjust the pH of the reaction solution to 4-6 with 0.5-2mol/L NaOH, react at 500-800rpm and 30-50°C for 1-3h, add 50-80 parts by weight of anhydrous ethanol, and let stand for 1-3h , filtered with suction, washed with absolute ethanol for 2-5 times, vacuum dried at 40-70°C for 6-12h, and refrigerated at 0-8°C to obtain thiol chitosan. 4.如权利要求3所述电镀液的制备方法，其特征在于，所述巯基化合物为巯基化聚乙烯亚胺和/或N-乙酰-L-半胱氨酸；所述巯基化聚乙烯亚胺的制备方法如下：4. the preparation method of electroplating solution as claimed in claim 3, is characterized in that, described mercapto compound is mercapto-polyethyleneimine and/or N-acetyl-L-cysteine; Described mercapto-polyethyleneimine; The preparation method of amine is as follows: 取0.5-2重量份聚乙烯亚胺溶于无水乙醇中，加入1-4重量份巯基乙酸甲酯混合，在50-70℃、300-500rpm下搅拌6-10h，得混合液A，在0.06-0.09MPa真空度、40-60℃下减压浓缩至混合液A的1/5-1/3，加2-10重量份去离子水溶解，加入2-8重量份乙酸乙酯，得混合液B，在0.05-0.1MPa真空度、40-60℃下减压浓缩至混合液B的1/5-1/3，冷冻干燥，得到巯基化聚乙烯亚胺。Dissolve 0.5-2 parts by weight of polyethyleneimine in absolute ethanol, add 1-4 parts by weight of methyl thioglycolate and mix, and stir at 50-70° C. and 300-500 rpm for 6-10 hours to obtain mixed solution A. 0.06-0.09MPa vacuum degree, concentrated under reduced pressure at 40-60 ℃ to 1/5-1/3 of the mixed solution A, add 2-10 parts by weight of deionized water to dissolve, and add 2-8 parts by weight of ethyl acetate to obtain The mixed solution B is concentrated under reduced pressure to 1/5-1/3 of the mixed solution B at a vacuum degree of 0.05-0.1 MPa and 40-60° C., and freeze-dried to obtain the mercaptolated polyethyleneimine. 5.一种电镀液，其特征在于，采用权利要求1-4任一项所述方法制备而成。5. An electroplating solution, characterized in that it is prepared by the method of any one of claims 1-4. 6.如权利要求5所述电镀液的应用，其特征在于，所述电镀液用于塑料表面电镀。6 . The application of the electroplating solution according to claim 5 , wherein the electroplating solution is used for electroplating on plastic surfaces. 7 . 7.如权利要求6所述电镀液的应用，其特征在于，所述塑料表面电镀的方法，包括以下步骤：7. the application of electroplating solution as claimed in claim 6, is characterized in that, the method for described plastic surface electroplating, comprises the following steps: S1、预处理：先用丙酮和无水乙醇的混合物对塑料的表面进行室温清洗5-10min，所述丙酮和无水乙醇的质量比为1:(1-2)；再用40-60℃、pH＝7-8.5的碳酸钠水溶液清洗3-10min，再用pH＝5-6.5的醋酸室温下超声清洗1-3min，最后用30-50℃水清洗2-5min，得到预处理塑料；S1. Pretreatment: first, use a mixture of acetone and absolute ethanol to clean the surface of the plastic at room temperature for 5-10 minutes, and the mass ratio of the acetone to absolute ethanol is 1: (1-2); then use 40-60° C. , and pH=7-8.5 sodium carbonate aqueous solution for 3-10min, then use pH=5-6.5 acetic acid for ultrasonic cleaning at room temperature for 1-3min, and finally wash with 30-50 ℃ water for 2-5min to obtain pretreated plastic; S2、粗化：将预处理塑料放入30-50℃的膨润液中浸泡5-15min，再放入50-65℃的微蚀液中，在超声功率120-200W、超声频率20-40kHz下处理10-25min，得到微蚀塑料；S2. Roughening: Soak the pretreated plastic in the swelling solution at 30-50°C for 5-15min, and then put it into the micro-etching solution at 50-65°C. Lower treatment for 10-25min to obtain micro-etched plastic; S3、中和：将微蚀塑料浸入中和液中，在50-70℃、200-500rpm搅拌5-15min，所述中和液为硫酸与草酸的混合水溶液，其中硫酸为15-50wt％、草酸为1-5wt％，取出、用去离子水冲洗2-5min；S3, neutralization: immerse the micro-erosion plastic in the neutralization solution, stir at 50-70° C. and 200-500rpm for 5-15min, and the neutralization solution is a mixed aqueous solution of sulfuric acid and oxalic acid, wherein the sulfuric acid is 15-50wt%, Oxalic acid is 1-5wt%, take out and rinse with deionized water for 2-5min; S4、敏化：将中和后的塑料放入敏化液中，在30-50℃浸泡20-40min，所述敏化液由0.01-0.1wt％氯化钯、1-5wt％氯化亚锡、及浓度为20-40ml/L的30-40wt％盐酸和10-25wt％氯化钾、余量为去离子水混合而成；S4. Sensitization: put the neutralized plastic into a sensitizing solution, soak it at 30-50° C. for 20-40min, and the sensitizing solution is composed of 0.01-0.1wt% palladium chloride, 1-5wt% subchloride tin, 30-40wt% hydrochloric acid and 10-25wt% potassium chloride with a concentration of 20-40ml/L, and the balance is deionized water; S5、活化：将敏化后的塑料放在活化液中，在室温下、300-500rpm活化3-10min，所述活化液由1-5wt％硝酸银、0.5-2wt％氨水、2-10wt％乙二醛、0.5-3wt％三乙醇胺、余量为去离子水混合而成；S5. Activation: put the sensitized plastic in an activation solution, activate at room temperature and 300-500rpm for 3-10min, the activation solution is composed of 1-5wt% silver nitrate, 0.5-2wt% ammonia water, 2-10wt% Glyoxal, 0.5-3wt% triethanolamine and the balance are deionized water mixed; S6、电镀：将活化后的塑料放入到电镀液中进行电镀处理，电镀温度为20-30℃，电流密度为0.5-2.0A/dm2，电镀时间为20-50min；S6, electroplating: put the activated plastic into the electroplating solution for electroplating treatment, the electroplating temperature is 20-30°C, the current density is 0.5-2.0A/dm 2 , and the electroplating time is 20-50min; S7、成品：对电镀处理后的塑料放在温度为50-70℃下干燥1-3h，冷却至室温，得到塑料表面金属镀层。S7. Finished product: The plastic after electroplating is dried at a temperature of 50-70° C. for 1-3 hours, and cooled to room temperature to obtain a metal coating on the surface of the plastic. 8.如权利要求7所述电镀液的应用，其特征在于，所述膨润液由10-25wt％5-羧基苯并三唑、20-40wt％N-甲基吡咯烷酮、10-20wt％氢氧化钾、5-15wt％N,N-二甲基甲酰胺、余量为去离子水混合而成；所述微蚀液为20-30wt％磷酸、50-65wt％硫酸、3-8wt％MnO2、0.01-0.05wt％十六烷基三甲基溴化铵、0.1-1wt％三聚磷酸钠、余量为去离子水混合而成。8. The application of the electroplating solution according to claim 7, wherein the swelling solution is composed of 10-25wt% 5-carboxybenzotriazole, 20-40wt% N-methylpyrrolidone, 10-20wt% hydrogen Potassium oxide, 5-15wt% N,N-dimethylformamide, and the balance of deionized water are mixed; the micro-etching liquid is 20-30wt% phosphoric acid, 50-65wt% sulfuric acid, 3-8wt% MnO 2. 0.01-0.05wt% cetyltrimethyl ammonium bromide, 0.1-1wt% sodium tripolyphosphate, and the remainder are deionized water. 9.如权利要求7所述的塑料表面电镀的方法，其特征在于，所述塑料为聚碳酸酯塑料、ABS塑料、聚酰亚胺塑料中任意一种。9 . The method for electroplating on a plastic surface according to claim 7 , wherein the plastic is any one of polycarbonate plastic, ABS plastic, and polyimide plastic. 10 .
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