CN109811380B - Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic - Google Patents
Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic Download PDFInfo
- Publication number
- CN109811380B CN109811380B CN201910217077.7A CN201910217077A CN109811380B CN 109811380 B CN109811380 B CN 109811380B CN 201910217077 A CN201910217077 A CN 201910217077A CN 109811380 B CN109811380 B CN 109811380B
- Authority
- CN
- China
- Prior art keywords
- abs plastic
- graphene
- abs
- conductive
- plastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a method for processing a conductive surface before electroplating ABS (acrylonitrile butadiene styrene) plastic, which is characterized in that a graphene coating is directly coated on the surface of a plastic product by a certain means by utilizing the excellent conductivity and film-forming property of a graphene microchip, so that the surface of the insulated ABS plastic is endowed with certain conductivity. The ABS plastic coated with the graphene conductive layer on the surface, which is prepared by the method, can be directly electroplated, complex and tedious procedures such as coarsening, sensitization, activation, chemical plating and the like in the traditional process are omitted, the ABS plastic is safer, more environment-friendly, simple and easy to implement, the process flow and the cost are greatly shortened, and the ABS plastic is suitable for industrial electroplating of ABS plastics with different shapes and sizes and has important practical application value. The graphene conducting layer coated on the ABS plastic surface by the method is uniform and continuous, has good adhesive force, and can be directly electroplated.
Description
Technical Field
The invention belongs to the technical field of graphene technology and plastic surface treatment, and particularly relates to a conductive surface treatment method before ABS plastic electroplating.
Background
In recent years, with the progress of science and technology and the continuous emergence of novel materials, the application of non-metal materials such as plastic, glass, ceramic, gypsum and the like in industry and daily life is more and more extensive, and a plurality of products made of metal are replaced by products such as plastic and the like, so that the weight and the cost of the products are greatly reduced. However, plastics also have certain disadvantages: non-conducting, non-heat conducting, non-wear-resistant, easy to deform, non-pollution resistant, lack of metal luster and aesthetic property, and the like, thereby limiting the application range to a certain extent. If a layer of metal is plated on the surface of the plastic, the defects of the plastic can be compensated, and the service performance of the plastic is greatly improved. Because the plastic cannot conduct electricity, a metal layer can be obtained after the surface of the plastic is treated by a special method, so that the plastic not only has the characteristic of light weight, but also has the properties of metal, such as conductivity, wear resistance, heat conductivity and the like. Therefore, the metallization process of the plastic surface has gained wide attention and has been rapidly developed, and has been widely applied in the fields of shielding technology, microelectronic technology, electrochemical protection, printed circuit board, and the like.
Currently, the five most widely used general plastics include: polyethylene (PE), polypropylene (PP), Polystyrene (PS), polyvinyl chloride (PVC) and ABS. Wherein, the ABS engineering plastic is terpolymer formed by copolymerizing acrylonitrile, butadiene and styrene, and Polybutadiene (PB) is dispersed in a polyacrylonitrile-styrene phase (SAN) by a branch phase. Therefore, the ABS resin has the excellent performances of three monomers, not only has good toughness, chemical stability, lower price, impact resistance, heat resistance, low temperature resistance and excellent electrical performance, but also has the characteristics of easy processing, stable product size, good surface gloss and the like, is easy to coat and color, can be subjected to secondary processing such as surface spraying metal, electroplating, welding, hot pressing, bonding and the like, is widely applied to the industrial fields such as machinery, aerospace, automobiles, shipbuilding, electronic appliances, instruments and meters, bathroom accessories, textiles, buildings and the like, and is a thermoplastic engineering plastic with extremely wide application.
In order to improve the aesthetic property, the electrical and thermal conductivity, the wear resistance, the corrosion resistance and the like of the ABS plastic, the ABS workpiece is generally required to be electroplated. ABS plastic plated articles have properties of both plastic and metal: it has small specific weight, good corrosion resistance, simple and convenient forming, metallic luster and metallic texture, and also has the characteristics of electric conduction, magnetic conduction, welding and the like. Because the metal plating layer has higher stability to external factors such as light, atmosphere and the like, after the plastics are plated with metal, the plastics can be prevented from aging, and the service life of the plastic part is prolonged. With the rapid development of industry and the increasingly wide application of plastic electroplating, the surface decorative coating becomes one of the important means of surface decoration in plastic products. The ABS plastic can enhance the strength property of the ABS plastic through electroplating, has better chemical stability and conductivity and decorative property, further expands the application field, and can be applied to the fields of electronic industry, medical instruments, instruments and meters, automobile accessories, mechanical parts, daily necessities, indoor decoration and the like.
Electroplating is widely carried out on the surfaces of plastics such as ABS, polypropylene, polysulfone, polycarbonate, nylon, phenolic glass fiber reinforced plastics, polystyrene and the like at home and abroad. By "plastic plating" is meant a process of applying a metal coating to the surface of a plastic in the form of a combination of electroplating and electroless plating. The processing can keep the advantages of high production efficiency, low price and light weight of the plastic, and simultaneously, the plastic has the characteristics of heat conduction, ageing resistance, electric conduction, metal appearance and the like, so that the plastic electroplating process is widely applied to the aspects of light industrial products, machine tool buttons, optical instruments, electronics and the like. In particular, the functions embodied in the aspects of functionality, engineering and the like have been raised to one of a series of indispensable 'processes' of related products. However, when engineering plastics with different functions are used, an important problem is faced: plastic as a non-conductor is difficult to be directly electroplated, so a transition coating needs to be formed on the plastic substrate before electroplating to connect the substrate and the metal layer so as to ensure good appearance and bonding force. In order to plate a metal layer on a plastic surface, a conductive pretreatment is usually required on the plastic surface, and the common treatment methods can be divided into two categories: one is a dry method, mainly referring to metal spraying and vacuum coating, the vacuum coating is to directly deposit a metal layer on a plastic substrate by sputtering or evaporation coating, the binding force of the vacuum coating is ensured by plasma etching, the applicability is limited, and the vacuum coating can only be applied to a plurality of thermoplastic plastics; the other is a wet method, which comprises directly coating conductive adhesive on the surface of the plastic, or treating the surface of the plastic by chemical roughening, sensitizing, activating and chemical copper plating or nickel plating, so that the insulated plastic has certain conductivity. The surface treatment methods have high requirements on equipment, high cost, high pollution and complicated procedures, and have certain selectivity and limitation on the treated plastics. In order to solve the restriction in the coarsening and activation processes, the engineering plastics such as ABS, PI, PA, PET, PVC, PC and the like are subjected to chromium-free coarsening and palladium-free activation before chemical plating at home and abroad The process is researched a lot, aiming at different plastic base materials, the coarsening liquid is mainly MnO2、H2SO4And the three systems of NaOH can be directly activated without palladium after coarsening, and can also be metalized after grafting organic ligands rich in active functional groups such as chitosan, polyacrylic acid, polypyrrole, silane coupling agent and the like on the surface.
Conventional metallization procedures are successful and have become popular, which is undoubted. Currently, the electroplating process commonly used for ABS plastics can be simply divided into two major steps: the first step is the pretreatment of plastic electroplating, namely preplating, a conductive film is covered on the surface of ABS plastic by chemical plating, and the general flow is as follows: degreasing, coarsening, neutralizing, sensitizing, activating, reducing and chemical nickel; the second step is plastic electroplating, namely further electroplating is carried out on the basis of chemical plating to obtain better combination degree and glossiness, and the general flow is as follows: pre-plating nickel, bright copper, semi-bright nickel, nickel seal and bright chromium. A large amount of strong oxidizing solutions such as chromic anhydride and sulfuric acid are used in the coarsening process of the traditional chemical plating, a large amount of heavy metal salts such as stannous salt and trivalent titanium salt are used in the sensitizing process, the activating solution used in the activating process contains precious metals such as gold, silver, platinum and palladium, the process is complicated, the cost is high, and a large amount of wastewater and heavy metal ions are generated in the pre-plating process, such as Cr (VI) which is easy to cause serious damage to human bodies and the environment. Employees working in microetching or chrome plating facilities for long periods of time are infected with cr (vi), and in severe cases even nasal septal perforation and skin cancer can occur. The surface metallization is carried out on tens of thousands tons of engineering plastics every year after microetching by a chromic anhydride-sulfuric acid system, and the environmental pollution caused by the microetching is obvious. Therefore, a more simple and environment-friendly pre-plating process needs to be researched, the process flow is simplified, and heavy metal salt and noble metal are prevented from being used in large quantities, so that the pre-plating process of the ABS plastic is more economic and environment-friendly. In addition, the research and development of the chromium-free pre-plating process not only can meet the requirements of modern industry, but also is necessary and urgent for protecting the human body and the living environment.
Based on the problems of the electroless plating process, there are active attempts to eliminate the direct plating technique of the non-conductive surface of the electroless plating process. There has been a study of treating a non-conductive surface with colloidal palladium to form a semiconductive film of colloidal Pd particles on the non-conductive surface, and then placing the film in a plating bath for plating. It has been found that by growing the coating from the conductive surface along the catalyzed non-conductive surface, the electrodeposition process is relatively slow, the coating thickness is non-uniform, the coating is thickest at the interface adjacent the conductive surface and is thinner furthest from the interface. Obviously, this process is not suitable, but it gives the introduction of direct plating, and the relevant researchers have taken the lead to carry out a lot of research on direct plating, and make the direct plating process continuously perfect and have operability and practicability.
Therefore, in addition to the electroless copper plating or nickel plating on the plastic surface by the above conventional methods, a great deal of effort has been made in recent years for improving the plastic electroplating process, and there have been researches to form a conductive transition coating on a plastic substrate by loading a conductive polymer material such as polypyrrole, polyaniline, polythiophene, PEDOT-PSS, and polyphenylene sulfide on the plastic surface. There are studies showing that by using certain concentrations of KMnO 4Concentrated H2SO4And emulsifying agent for coarsening ABS plastic, pyrrole as monomer, FeCl3The method is characterized in that a conductive polypyrrole film is formed on the surface of plastic by an oxidation polymerization method as a main oxidant and a dopant, and then electroplating is directly carried out. There are three main forms of electroplating that have been shown to be carried out directly on plastic substrates: directly electroplating conductive polymer, namely coating a layer of polymer conductive material on the surface of a plastic substrate and then electroplating; Pd/Sn activated direct electroplating, namely forming a metal Pd layer on the surface of the plastic by a Futuron process invented by the Anmet company for direct electroplating or carrying out electroplating after the Pd layer catalyzes copper to replace tin, wherein steps are saved, but the content of palladium in a colloid palladium activation solution required by the activation process is higher, and the cost is also higher; directly electroplating carbon particle suspension comprising carbon particles, binder, surfactant, water-soluble polymer compound, etc. the carbon particles including graphite particles and carbon black particles by spraying, dipping and coatingThe method comprises adhering carbon particles with conductivity to plastic substrate, and performing acid treatment and microetching treatment to directly perform electroplating. It has also been shown that a catalyzed non-conductive surface is treated with a chalcogenide solution to convert it to a conductive catalytic metal chalcogenide conversion coating (e.g., PdS) as a conductive substrate layer for direct plating. However, these methods have high cost and harsh operating conditions, and are only suitable for experimental research and are not suitable for industrial mass production.
Graphene, as a novel conductive carbon nanomaterial, was successfully prepared in 2004, and has caused a hot trend in research by researchers at home and abroad due to its excellent thermal conductivity (5300Wm-1K-1, the thermal conductivity is ten times that of copper), electrical conductivity (the current mobility at room temperature is up to 15000m2V-1S-1), optical properties (the light transmittance is up to 97.7%), perfect quantum tunneling effect, half-integer quantum hall effect, room-temperature ferromagnetism, and super-strong mechanical properties (tensile strength 130GPa, young modulus is about 1 TPa). The graphene has great application potential in the fields of conductive coatings and composite materials due to excellent photoelectric properties and super-strong mechanical properties. Therefore, if the graphene material can be successfully coated on the surface of the plastic product by a certain process method, the plastic product can complete the pre-plating process under the condition of no heavy metal and noble metal, and the development and practical application of the graphene technology can be promoted. Compared with a conductive polymer and traditional carbon particles, the graphene material has better conductivity and mechanical property, can be self-assembled to form a film on the surface of plastic by modifying the graphene material, and is easy to cover the surface of the plastic due to the unique two-dimensional crystal structure of the graphene, and has good adhesive force. Research shows that the conductive carbon black has conductivity, film forming performance and metal ion adsorbing performance to form conductive layer on the surface of ABS plastic and subsequent copper electroplating. Although the process method avoids the processes of surface roughening, activation and the like and reduces the use of chromic acid, hydrochloric acid and the like, the steps are still too complicated, the conductive blackening is easy to agglomerate, the conductivity of the conductive black is far inferior to that of a graphene material, carbon black particles need to be oxidized and loaded with metal nano particles, expensive noble metal salt and an insulating dispersing wetting agent are used in the process, the cost cannot be controlled well, and the conductivity of the coating is greatly influenced. Researches show that graphene and plastic resin such as ABS, PC and the like are put into a mixing roll to be stirred and mixed, then the mixture is extruded and granulated through a screw extruder, and finally the plastic electroplated part with micropores on the surface is obtained through injection molding. When the plastic electroplating workpiece is electroplated by using the method, chemical pretreatment can be cancelled, the electroplating process is shortened, and the environmental pollution is reduced. However, in consideration of the problem of dispersibility of graphene materials in resin matrices, this method is only applicable to graphene oxide and derivatives thereof as inorganic fillers, and has narrow applicability. The conductivity of the plastic workpiece prepared by the method is not obviously improved, only a plurality of micropores are formed on the surface of the plastic workpiece, a roughening step is mainly omitted in the electroplating process, and other excellent properties of the graphene material are not fully utilized in the plastic electroplating process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a conductive surface treatment method before ABS plastic electroplating, and solves the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problem is as follows: provides a method for processing a conductive surface before electroplating ABS plastic, which comprises the following steps:
(1) preparing oil removing alkali, and carrying out surface oil removing treatment on the ABS plastic;
(2) preparing graphene composite conductive slurry: taking 10-20 parts of conductive filler, 300-550 parts of mixed solvent, 10-25 parts of auxiliary agent and 10-30 parts of binder by mass, grinding, mixing and modifying to obtain composite conductive slurry;
wherein the conductive filler comprises at least one of graphene, carbon nanotubes, conductive carbon black, expanded graphite and conductive carbon fibers; the mixed solvent is formed by mixing an organic solvent and water in a volume ratio of 1: 1-8: 1, wherein the organic solvent comprises at least one of ethanol, ethylene glycol, glycerol, isopropanol, terpineol, methanol, formic acid, cyclohexanone, toluene, DMF, NMP, acetone, dimethyl sulfoxide, tetrahydrofuran and chloroform; the auxiliary agent comprises 1-5 parts by mass of a dispersing agent, 1-2 parts by mass of a defoaming agent, 10-15 parts by mass of a wetting agent and 1-2 parts by mass of a thickening agent;
(3) And coating the graphene composite conductive slurry on the surface of the ABS plastic and drying.
In a preferred embodiment of the present invention, the graphene is single-layer graphene, few-layer graphene, or multi-layer graphene.
In a preferred embodiment of the present invention, the oil removing alkali solution in step (1) is prepared from sodium hydroxide, sodium phosphate, sodium carbonate, an emulsifier and distilled water, wherein the emulsifier comprises at least one of OP emulsifier, detergent and surfactant.
In a preferred embodiment of the present invention, the concentration of sodium hydroxide in the degreasing alkaline solution is 20-80 g/L, the concentration of sodium phosphate is 30-45 g/L, the concentration of sodium carbonate is 15-50 g/L, and the concentration of the emulsifier is 1-5 ml/L.
In a preferred embodiment of the invention, the oil removing treatment in the step (1) is to soak the ABS plastic in an oil removing alkali solution, treat the ABS plastic in a constant temperature water bath at 35-75 ℃ for 10-40 min, then take out the ABS plastic, clean the ABS plastic with distilled water to remove the residual oil removing alkali solution, and dry the ABS plastic to obtain the oil removing ABS plastic product.
In a preferred embodiment of the present invention, the binder is at least one of starch, protein, water-based acrylic resin, polyurethane resin, vinyl acetate resin, modified epoxy resin, hydroxypropyl methylcellulose, ethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol.
In a preferred embodiment of the present invention, the step (2) is performed by grinding, mixing and modifying using a grinding apparatus, which includes a planetary ball mill, a sand mill, a basket mill, a three-roll mill, a two-roll mill, a colloid mill or a horizontal ball mill.
In a preferred embodiment of the present invention, the grinding and mixing time in the step (2) is 3 to 48 hours.
In a preferred embodiment of the present invention, the method for applying the graphene composite conductive paste on the surface of the ABS plastic in step (3) includes a dip coating method, a spin coating method, a spray coating method, a drop coating method or a plasma spray coating method.
In a preferred embodiment of the present invention, the step (3) adopts forced air drying, vacuum drying, natural air drying, desiccator drying or infrared lamp drying.
Compared with the background technology, the technical scheme has the following advantages:
compared with the first improvement, the pre-plating solution is prepared by taking graphene oxide, an organic solvent and water as raw materials, the microstructure and the components of the surface of the ABS plastic are changed by utilizing the swelling and micro-corrosion effect of the organic solvent on the ABS plastic, the hydrophilicity and the adhesion of the ABS plastic are improved, so that graphene oxide micro-sheets are attached to the surface of the plastic and assembled into a film, an ABS product with a surface coated with a reduced graphene oxide conducting layer is obtained after reduction, the subsequent electroplating can be carried out, although the pre-plating process of the ABS plastic is greatly simplified, the pre-plating treatment time is difficult to control, the ABS plastic is easy to scratch or damage in the organic mixed solvent, and the operation process needs great attention.
The two-dimensional graphene material with excellent conductivity is used as a precursor, a precious metal material or a toxic substance is not used, the cost is lower, the environment is more environment-friendly, and the conductivity is better. The two-dimensional graphene material can be well dispersed in a green solvent by a simple one-step grinding, mixing and modifying method like ultra-thin paper, and then under the synergistic action of a water-soluble binder, a uniform and firm graphene conducting layer is formed on the surface of the ABS plastic by technological means such as spraying and dip-coating, no damage to the ABS plastic in any form can be caused, the operation is very simple and convenient, the automatic treatment can be performed on an industrial production line, the conducting treatment process before electroplating the ABS plastic can be greatly simplified, the obtained product has excellent conducting performance, and the electroplating can be directly performed.
The preparation process is simple and easy to implement, has higher efficiency, is safer and more environment-friendly, omits a series of complicated and toxic steps to the environment and the health of operators, such as coarsening, neutralization, sensitization, activation, reduction, chemical nickel and the like in the prior art, and is different from the traditional melt blending method;
The formula of the conductive treatment solution for the surface of the ABS plastic is safe and environment-friendly, the cost is low, the graphene material with lower price is innovatively used for replacing expensive materials such as heavy metal salt, precious metal, conductive polymer and the like, the organic solvent and water are used as mixed solvents, and the prepared pretreatment solution has stable property, is easy to store, has wide application range, can be repeatedly used and is convenient for subsequent recovery treatment;
the graphene conductive layer coated on the surface of the ABS plastic product by the process method is uniform and continuous, has good adhesive force, and endows the ABS plastic product with excellent conductivity and glossiness, so that the ABS plastic product can be directly subjected to subsequent electroplating treatment, and the process method is favorable for promoting wider application of the ABS plastic product and further development of graphene technology.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention;
fig. 2(a) is an apparent image of the ABS plastic article coated with the graphene composite conductive coating prepared in example 1; fig. 2(b) is an appearance picture of the ABS plastic product coated with the graphene composite conductive coating prepared in example 1 after electroplating;
FIG. 3(a) is an apparent image of the ABS plastic product coated with the graphene conductive coating prepared in example 2; FIG. 3(b) is an electroplated appearance picture of the ABS plastic product coated with the graphene conductive coating prepared in example 2;
Fig. 4(a) is an apparent image of the ABS plastic article coated with the graphene composite conductive coating prepared in example 3; fig. 4(b) is an electroplated appearance picture of the ABS plastic product coated with the graphene composite conductive coating prepared in example 3;
fig. 5(a) is an apparent image of the ABS plastic article coated with the graphene composite conductive coating prepared in example 4; fig. 5(b) is an electroplated appearance picture of the ABS plastic product coated with the graphene composite conductive coating prepared in example 4;
fig. 6(a) is an apparent image of the ABS plastic article coated with the graphene composite conductive coating prepared in example 5; FIG. 2(b) is an image of the ABS plastic product coated with the graphene composite conductive coating prepared in example 5 after electroplating;
fig. 7(a) is an apparent image of the ABS plastic article coated with the graphene composite conductive coating prepared in example 6; fig. 7(b) is an appearance picture of the ABS plastic product coated with the graphene composite conductive coating prepared in example 6 after electroplating.
Detailed Description
Example 1
Referring to fig. 1, the method for processing the conductive surface before the ABS plastic is electroplated according to the embodiment includes the following steps:
(1) preparing oil removing alkali, and carrying out surface oil removing treatment on the ABS plastic;
Soaking the original ABS plastic product in degreasing alkali liquor to carry out constant-temperature water bath treatment, wherein the constant-temperature is 70 ℃, the degreasing treatment time is 30min, and then cleaning and drying the alkali liquor on the surface of the ABS plastic product by using distilled water for later use;
the oil removing alkali liquor is prepared by mixing and dissolving sodium hydroxide, sodium phosphate, sodium carbonate and an emulsifier in a certain ratio in distilled water, wherein the concentration of the sodium hydroxide is 20-80 g/L, the concentration of the sodium phosphate is 30-45 g/L, the concentration of the sodium carbonate is 15-50 g/L, and the concentration of the emulsifier is 1-5 mL/L; the emulsifier comprises at least one of OP emulsifier, detergent and surfactant, and the emulsifier adopted in the embodiment is the most common detergent in life.
(2) Preparing graphene composite conductive slurry: 190 parts of isopropanol and 120 parts of H2Taking O as a mixed solvent, taking 10 parts of graphene powder and 2 parts of multi-walled carbon nanotubes as conductive fillers, taking 5 parts of dispersing agent, 1 part of defoaming agent, 10 parts of wetting agent and 2 parts of thickening agent as auxiliary agents, taking 10 parts of waterborne acrylic resin as a binder, performing ultrasonic pre-dispersion, and then further grinding and mixing to prepare graphene composite conductive slurry; the graphene is a single layerGraphene, few-layer graphene, multi-layer graphene; grinding, mixing and modifying by using a grinding instrument, wherein the grinding instrument comprises a planetary ball mill, a sand mill, a basket mill, a three-roller mill, a two-roller mill, a colloid mill or a horizontal ball mill, and the grinding, mixing and modifying time is 3-48 h.
(3) Coating the graphene composite conductive slurry on the surface of the ABS plastic and drying;
spraying the graphene composite conductive slurry on the surface of the deoiled ABS plastic product through a spray gun, and drying to obtain the ABS plastic product coated with the graphene composite conductive coating on the surface, as shown in FIG. 2 (a). The graphene composite conductive layer coated on the ABS plastic product by the method is uniform and continuous, and has good conductivity and adhesive force.
(4) Electroplating the ABS plastic product coated with the graphene composite conductive coating, and coating the metal layer, so as to obtain a metallized ABS workpiece as shown in fig. 2 (b).
Example 2
Example 2 differs from example 1 in that:
(1) preparing oil removing alkali liquor, soaking an original ABS plastic product in the oil removing alkali liquor to perform constant-temperature water bath treatment, wherein the constant temperature is 70 ℃, the oil removing treatment time is 30min, and then cleaning and drying the alkali liquor on the surface of the ABS plastic product by using distilled water for later use;
(2) taking the following raw materials in parts by mass: 190 parts of isopropanol and 120 parts of H2Taking O as a mixed solvent, taking 15 parts of graphene powder as a conductive filler, taking 1 part of a dispersing agent, 1 part of a defoaming agent, 10 parts of a wetting agent and 1 part of a thickening agent as auxiliaries, taking 15 parts of water-based acrylic resin as a binder, performing ultrasonic pre-dispersion, and then further grinding and mixing to obtain graphene composite conductive slurry;
(3) Spraying the graphene composite conductive slurry on the surface of the deoiled ABS plastic product through a spray gun, and drying to obtain the ABS plastic product coated with the graphene conductive coating on the surface, as shown in FIG. 3 (a). The graphene conducting layer coated on the ABS plastic product by the method is uniform and continuous, and has good conductivity and adhesive force;
(4) electroplating the ABS plastic product coated with the graphene conductive coating, and coating the metal layer, so as to obtain a metallized ABS workpiece as shown in fig. 3 (b).
Example 3
Example 3 differs from example 1 in that:
(1) preparing oil removing alkali liquor, soaking an original ABS plastic product in the oil removing alkali liquor to perform constant-temperature water bath treatment, wherein the constant temperature is 70 ℃, the oil removing treatment time is 30min, and then cleaning and drying the alkali liquor on the surface of the ABS plastic product by using distilled water for later use;
(2) taking the following raw materials in parts by mass: 315 parts of ethanol and 200 parts of H2Taking O as a mixed solvent, taking 10 parts of graphene powder and 2 parts of multi-walled carbon nanotubes as conductive fillers, taking 1 part of dispersing agent, 2 parts of defoaming agent, 10 parts of wetting agent and 2 parts of thickening agent as auxiliary agents, taking 10 parts of waterborne acrylic resin as a binder, performing ultrasonic pre-dispersion, and then further grinding and mixing to prepare graphene composite conductive slurry;
(3) Soaking the degreased ABS plastic product in the graphene composite conductive slurry for coating treatment, wherein the dip-coating time is 30s, and drying to obtain the ABS plastic product coated with the graphene composite conductive coating on the surface, as shown in fig. 4 (a). The graphene composite conductive layer coated on the ABS plastic product by the method is uniform and continuous, and has good conductivity and adhesive force;
(4) electroplating the ABS plastic product coated with the graphene composite conductive coating, and coating the metal layer, so as to obtain a metallized ABS workpiece as shown in fig. 4 (b).
Example 4
Example 4 differs from example 1 in that:
(1) preparing oil removing alkali liquor, soaking an original ABS plastic product in the oil removing alkali liquor to perform constant-temperature water bath treatment, wherein the constant temperature is 70 ℃, the oil removing treatment time is 30min, and then cleaning and drying the alkali liquor on the surface of the ABS plastic product by using distilled water for later use;
(2) taking the following raw materials in parts by mass: 315 parts of isopropanol and 200 parts of H2O as a mixed solvent, 15 parts of graphene powder and 5 parts of conductive carbon black as conductive fillersThe graphene composite conductive paste is prepared by performing ultrasonic pre-dispersion on a material, 6 parts of a dispersing agent, 1 part of a defoaming agent, 15 parts of a wetting agent and 1 part of a thickening agent as auxiliaries and 30 parts of aqueous acrylic resin as a binder, and then further grinding and mixing the materials;
(3) Soaking the degreased ABS plastic product in the graphene composite conductive slurry for coating treatment, wherein the dip-coating time is 90s, and drying to obtain the ABS plastic product coated with the graphene composite conductive coating on the surface, as shown in fig. 5 (a). The graphene composite conductive layer coated on the ABS plastic product by the method is uniform and continuous, and has good conductivity and adhesive force;
(4) electroplating the ABS plastic product coated with the graphene composite conductive coating, and coating the metal layer, so as to obtain a metallized ABS workpiece as shown in fig. 5 (b).
Example 5
Example 5 differs from example 1 in that:
(1) preparing oil removing alkali liquor, soaking an original ABS plastic product in the oil removing alkali liquor to perform constant-temperature water bath treatment, wherein the constant temperature is 70 ℃, the oil removing treatment time is 30min, and then cleaning and drying the alkali liquor on the surface of the ABS plastic product by using distilled water for later use;
(2) taking the following raw materials in parts by mass: 155 parts of isopropanol, 155 parts of ethanol and 200 parts of H2Taking O as a mixed solvent, taking 10 parts of graphene powder and 2 parts of multi-walled carbon nanotubes as conductive fillers, taking 5 parts of a dispersing agent, 2 parts of a defoaming agent, 10 parts of a wetting agent and 2 parts of a thickening agent as auxiliaries, taking 10 parts of waterborne acrylic resin as a binder, performing ultrasonic pre-dispersion, and then further grinding and mixing to prepare graphene composite conductive slurry;
(3) Spraying the graphene composite conductive slurry on the surface of the degreased ABS plastic product through a spray gun, and drying to obtain the ABS plastic product coated with the graphene composite conductive coating on the surface, as shown in FIG. 6 (a). The graphene composite conductive layer coated on the ABS plastic product by the method is uniform and continuous, and has good conductivity and adhesive force;
(4) electroplating the ABS plastic product coated with the graphene composite conductive coating, and coating the metal layer, so as to obtain a metallized ABS workpiece as shown in fig. 6 (b).
Example 6
Example 6 differs from example 1 in that:
(1) preparing oil removing alkali liquor, soaking an original ABS plastic product in the oil removing alkali liquor to perform constant-temperature water bath treatment, wherein the constant temperature is 70 ℃, the oil removing treatment time is 30min, and then cleaning and drying the alkali liquor on the surface of the ABS plastic product by using distilled water for later use;
(2) taking the following raw materials in parts by mass: 315 parts of ethanol, 90 parts of terpineol and 100 parts of H2Taking O as a mixed solvent, taking 15 parts of graphene powder and 3 parts of multi-walled carbon nanotubes as conductive fillers, taking 1 part of dispersing agent, 2 parts of defoaming agent, 10 parts of wetting agent and 2 parts of thickening agent as auxiliary agents, taking 10 parts of waterborne acrylic resin as a binder, performing ultrasonic pre-dispersion, and then further grinding and mixing to prepare graphene composite conductive slurry;
(3) Spraying the graphene composite conductive slurry on the surface of the deoiled ABS plastic product by using a spray gun, and drying to obtain the ABS plastic product coated with the graphene composite conductive coating on the surface, as shown in FIG. 7 (a). The graphene composite conductive layer coated on the ABS plastic product by the method is uniform and continuous, and has good conductivity and adhesive force;
(4) electroplating the ABS plastic product coated with the graphene composite conductive coating, and coating the metal layer, so as to obtain a metallized ABS workpiece as shown in fig. 7 (b).
As shown in fig. 2 to 7, in 6 embodiments of the present invention, the graphene composite conductive coating coated on the surface of the ABS plastic product is uniform, continuous, very smooth, and has good adhesion. The graphene composite conductive coating also has certain silver gray metallic luster, and the brightness, the wear resistance and the corrosion resistance of plastic products such as ABS are greatly improved while the plastic products such as ABS are endowed with conductivity. As shown in fig. 2 to 7, as shown in fig. b, all the ABS plastic products coated with the graphene composite conductive coating on the surface according to 6 embodiments of the present invention can be subjected to subsequent electroplating, and the metal plating layer is uniform and smooth, and is as bright as a mirror surface, and does not fall off or deform, so that a series of excellent properties such as aesthetic property, wear resistance, thermal conductivity, and stain resistance are imparted to the ABS plastic products, thereby further expanding the application range of the ABS plastic products. Therefore, after the graphene conducting layer is coated on the surface of the plastic product by the method, the plastic product can be directly subjected to subsequent electroplating, and the surface treatment process before plastic plating is greatly simplified.
Table 1 shows the surface resistivity, the adhesion of the graphene conductive layer, and the adhesion of the metal plating layer of the ABS product coated with the graphene conductive layer, which are obtained in 6 specific examples of the present invention.
TABLE 1
In summary, the test results of the surface resistivity, the adhesion of the graphene composite conductive layer and the adhesion of the metal plating layer of the ABS product coated with the graphene composite conductive layer in table 1 show that the method for treating the conductive surface before the ABS plastic is electroplated is feasible. Firstly, after selecting a proper solvent and an auxiliary agent, a dispersant molecule can be loaded on the carbon nano materials such as the graphene nanoplatelets by a one-step grinding, mixing and modifying method, so that the carbon nano materials such as the graphene nanoplatelets and the like are effectively prevented from agglomerating and settling in the solvent, stable graphene composite conductive slurry is formed, and the bonding property between the carbon nano materials and a plastic base material can be improved by the connecting material in the slurry. And then, adhering the graphene composite conductive slurry to the surface of the plastic product by using technological methods such as spraying, dip coating, spin coating, drop coating and the like, and forming a graphene conductive layer on the surface of the plastic product, so that the insulated plastic product has good conductivity, thereby completing the pre-plating process and facilitating the direct subsequent electroplating of the plastic product. The method successfully realizes the chromium-free pre-plating of the ABS plastic product and greatly simplifies the pre-plating process. The graphene conducting layer coated on the surface of the ABS product by the method is uniform and continuous, has good adhesive force and lower surface resistivity, and meets the requirements of industrial production and application. The ABS plastic product coated with the graphene composite conductive layer can be directly subjected to subsequent electroplating treatment, and a metal coating which is uniform, bright and excellent in adhesive force is successfully plated on the surface of the product, so that more possibilities are provided for the application of the ABS product. Therefore, the technology of the invention can be applied to the industrial large-scale preparation of ABS electroplating products.
It will be appreciated by those skilled in the art that the same or similar technical effects as those of the above embodiments can be expected when the technical parameters of the present invention are changed within the following ranges:
the binder is at least one of starch, protein, water-based acrylic resin, polyurethane resin, vinyl acetate resin, modified epoxy resin, hydroxypropyl methyl cellulose, ethyl cellulose, carboxymethyl cellulose and polyvinyl alcohol.
The method for coating the graphene composite conductive slurry on the surface of the ABS plastic in the step (3) comprises a dip coating method, a spin coating method, a spraying method, a dripping coating method or a plasma spraying method.
And (3) adopting forced air drying, vacuum drying, natural air drying, drier drying or infrared lamp drying.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, and all equivalent variations and modifications made within the scope of the present invention and the content of the description should be included in the scope of the present invention.
Claims (11)
1. A method for processing the conductive surface before electroplating ABS plastic is characterized by comprising the following steps:
(1) preparing oil removing alkali, and performing surface oil removing treatment on the ABS plastic;
(2) preparing graphene composite conductive slurry: taking 15-20 parts of conductive filler, 300-550 parts of mixed solvent, 10-25 parts of auxiliary agent and 10-30 parts of binder by mass, grinding, mixing and modifying to obtain composite conductive slurry;
Wherein the conductive filler is graphene; or the conductive filler is graphene, and at least one of carbon nano tube, conductive carbon black, expanded graphite and conductive carbon fiber is added; the mixed solvent is formed by mixing an organic solvent and water in a volume ratio of 1: 1-8: 1, wherein the organic solvent comprises at least one of ethanol, ethylene glycol, glycerol, isopropanol, terpineol and methanol; the auxiliary agent comprises 1-5 parts by mass of a dispersing agent, 1-2 parts by mass of a defoaming agent, 10-15 parts by mass of a wetting agent and 1-2 parts by mass of a thickening agent; the binder is at least one of starch, protein, water-based acrylic resin, polyurethane resin, vinyl acetate resin, modified epoxy resin, hydroxypropyl methyl cellulose, ethyl cellulose, carboxymethyl cellulose and polyvinyl alcohol;
(3) and coating the graphene composite conductive slurry on the surface of the ABS plastic and drying.
2. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: the graphene is single-layer graphene, few-layer graphene or multi-layer graphene.
3. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: the oil removing alkali liquor in the step (1) is prepared from sodium hydroxide, sodium phosphate, sodium carbonate, an emulsifier and distilled water, wherein the emulsifier is an OP emulsifier.
4. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: the oil removing alkali liquor in the step (1) is prepared from sodium hydroxide, sodium phosphate, sodium carbonate, an emulsifier and distilled water, wherein the emulsifier is a detergent.
5. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: the oil removing alkali liquor in the step (1) is prepared from sodium hydroxide, sodium phosphate, sodium carbonate, an emulsifier and distilled water, wherein the emulsifier is a surfactant.
6. The method for treating the conductive surface of the ABS plastic before electroplating according to any one of claims 3-5, wherein the method comprises the following steps: the concentration of sodium hydroxide in the oil removing alkali liquor is 20-80 g/L, the concentration of sodium phosphate is 30-45 g/L, the concentration of sodium carbonate is 15-50 g/L, and the concentration of an emulsifier is 1-5 ml/L.
7. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: and (2) the oil removing treatment in the step (1) is to soak the ABS plastic in oil removing alkali liquor, treat the ABS plastic in a constant-temperature water bath at 35-75 ℃ for 10-40 min, take out the ABS plastic, clean the ABS plastic with distilled water to remove residual oil removing alkali liquor, and dry the ABS plastic to obtain an oil removing ABS plastic product.
8. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: and (3) grinding, mixing and modifying by using a grinding instrument in the step (2), wherein the grinding instrument comprises a planetary ball mill, a sand mill, a basket mill, a three-roller mill, a two-roller mill, a colloid mill or a horizontal ball mill.
9. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: and (3) grinding and mixing time of the step (2) is 3-48 h.
10. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: the method for coating the graphene composite conductive slurry on the surface of the ABS plastic in the step (3) comprises a dip coating method, a spin coating method, a spraying method, a dripping coating method or a plasma spraying method.
11. The method for treating the conductive surface of the ABS plastic before electroplating according to claim 1, wherein the method comprises the following steps: and (3) adopting forced air drying, vacuum drying, natural air drying, drier drying or infrared lamp drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910217077.7A CN109811380B (en) | 2019-03-21 | 2019-03-21 | Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910217077.7A CN109811380B (en) | 2019-03-21 | 2019-03-21 | Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109811380A CN109811380A (en) | 2019-05-28 |
| CN109811380B true CN109811380B (en) | 2022-06-10 |
Family
ID=66609825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910217077.7A Active CN109811380B (en) | 2019-03-21 | 2019-03-21 | Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109811380B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110093645A (en) * | 2019-05-31 | 2019-08-06 | 厦门大学 | Plastic electroplating method |
| CN111607812A (en) * | 2020-04-29 | 2020-09-01 | 杭州临安兴旺电镀有限公司 | Environment-friendly electroplating method for plastic workpiece |
| CN112657806A (en) * | 2020-12-15 | 2021-04-16 | 安徽恒茂宜高电镀科技有限公司 | ABS engineering plastic surface metal layer and preparation method thereof |
| CN113817203A (en) * | 2021-09-22 | 2021-12-21 | 华南理工大学 | Method for preparing Cu-CNTs super-hydrophobic coating on plastic surface |
| CN114892230A (en) * | 2022-05-25 | 2022-08-12 | 上海瑞尔实业有限公司 | Plastic surface electroplating process |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030138A (en) * | 2012-12-17 | 2013-04-10 | 鸿纳（东莞）新材料科技有限公司 | Folding preventing less-layer graphene powder, components of composite material thereof, and application |
| CN103113786A (en) * | 2013-03-07 | 2013-05-22 | 苏州牛剑新材料有限公司 | Graphene conductive ink and preparation method thereof |
| CN105001716A (en) * | 2015-06-30 | 2015-10-28 | 中国科学院山西煤炭化学研究所 | Graphene-based low resistance conductive printing ink and preparation method thereof |
| CN107266695A (en) * | 2016-04-04 | 2017-10-20 | 波音公司 | The method that there is the process unit on durable metal surface in the polymeric substrates that addition is formed and such a process unit is formed |
| CN107674505A (en) * | 2017-11-23 | 2018-02-09 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of Graphene conductive ink and preparation method thereof |
| CN108530996A (en) * | 2018-05-25 | 2018-09-14 | 北京航科航天科技有限公司 | A kind of one-step method prepares graphene-based water-soluble conducting ink and preparation method thereof |
| CN108834309A (en) * | 2018-08-30 | 2018-11-16 | 陈伟元 | A kind of graphene metallization solution and the preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928773B (en) * | 2017-05-08 | 2020-09-25 | 华侨大学 | Graphene composite conductive ink for ink-jet printing and preparation method thereof |
| CN108425138B (en) * | 2018-05-11 | 2020-05-05 | 华侨大学 | Surface treatment method for ABS plastic electroplating |
| CN109161273A (en) * | 2018-09-14 | 2019-01-08 | 安庆市泽烨新材料技术推广服务有限公司 | Frosting conductive coating |
-
2019
- 2019-03-21 CN CN201910217077.7A patent/CN109811380B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030138A (en) * | 2012-12-17 | 2013-04-10 | 鸿纳（东莞）新材料科技有限公司 | Folding preventing less-layer graphene powder, components of composite material thereof, and application |
| CN103113786A (en) * | 2013-03-07 | 2013-05-22 | 苏州牛剑新材料有限公司 | Graphene conductive ink and preparation method thereof |
| CN105001716A (en) * | 2015-06-30 | 2015-10-28 | 中国科学院山西煤炭化学研究所 | Graphene-based low resistance conductive printing ink and preparation method thereof |
| CN107266695A (en) * | 2016-04-04 | 2017-10-20 | 波音公司 | The method that there is the process unit on durable metal surface in the polymeric substrates that addition is formed and such a process unit is formed |
| CN107674505A (en) * | 2017-11-23 | 2018-02-09 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of Graphene conductive ink and preparation method thereof |
| CN108530996A (en) * | 2018-05-25 | 2018-09-14 | 北京航科航天科技有限公司 | A kind of one-step method prepares graphene-based water-soluble conducting ink and preparation method thereof |
| CN108834309A (en) * | 2018-08-30 | 2018-11-16 | 陈伟元 | A kind of graphene metallization solution and the preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109811380A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109811380B (en) | Conductive surface treatment method before electroplating of ABS (acrylonitrile butadiene styrene) plastic | |
| CN108425138B (en) | Surface treatment method for ABS plastic electroplating | |
| CA2426648C (en) | Plating method of metal film on the surface of polymer | |
| WO2020238144A1 (en) | Plastic electroplating method | |
| JP4993074B2 (en) | Continuous electroless plating method | |
| CN101160632B (en) | Process for producing metal conductive film | |
| CN105603477B (en) | A kind of ABS plastic electro-coppering pretreatment process | |
| CN107354752B (en) | Surface-coated silver F-12 conductive fiber and preparation method thereof | |
| TWI438301B (en) | Metal plated article of molded form and method for producing it | |
| CN110029382A (en) | A kind of process of surface treatment and its related directly electroplating technology for being directly electroplated | |
| CN114260450B (en) | Silver-plated micron-sized particles and preparation method and application thereof | |
| Wang et al. | A laser curable palladium complex ink used for fabrication of copper pattern on polyimide substrate | |
| TW201732103A (en) | Conductive textile and manufacturing method thereof | |
| CN104762614B (en) | A kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process | |
| JP5780635B2 (en) | Plating | |
| CN111705357B (en) | ABS plastic surface coating deplating process | |
| KR20090104012A (en) | Plated article and method for producing the same | |
| CN112482024A (en) | Preparation method of copper-plated carbon fabric electromagnetic shielding material | |
| JP6072343B1 (en) | Hydraulic transfer film for electroless plating | |
| CN111962035A (en) | Magnesium-based or aluminum-based filter cavity coating and preparation method thereof | |
| JP5310993B2 (en) | Plating undercoating on styrene resin substrate and plated product of styrene resin substrate produced using the same | |
| CN112010572A (en) | Conductive glass fiber and preparation method thereof | |
| JP6284536B2 (en) | Coating composition for electroless plating | |
| CN114226725B (en) | Silver-modified micron-sized particles, and preparation method and application thereof | |
| WO2017050272A1 (en) | Thin film coating layer composition and coating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |