CN111101095A - Chromium-free metallization method for plastic substrate - Google Patents
Chromium-free metallization method for plastic substrate Download PDFInfo
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- CN111101095A CN111101095A CN202010028198.XA CN202010028198A CN111101095A CN 111101095 A CN111101095 A CN 111101095A CN 202010028198 A CN202010028198 A CN 202010028198A CN 111101095 A CN111101095 A CN 111101095A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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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
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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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
Abstract
The invention belongs to the field of metallization of the surface of an insulating base material, and particularly relates to a chromium-free metallization method for a plastic base material. The method for the chromium-free metallization of the plastic base material mainly comprises the process flows of base material extrusion molding, base material surface treatment, direct current sputtering metallization, electroplating and the like. The method for the chromium-free metallization of the plastic base material provided by the invention adds MgAl into the plastic base material2O4And ZnAl2O4The prepared plastic product not only can keep better adhesive force of the metal layer, but also can realize the functions of quickly dissipating heat and keeping the temperature of the conductive metal layer close to constant in practical application, the surface treatment process is simple, and the discharge of waste water is greatly reduced.
Description
Technical Field
The invention relates to the field of metallization of the surface of an insulating base material, in particular to a chromium-free metallization method for a plastic base material.
Background
The plastic has the characteristics of higher impact strength, good processing formability, corrosion resistance, light weight and the like, and is metalized, so that the plastic not only keeps the original characteristics of the plastic, but also has the performances of conductivity, permeability, decoration, weldability and the like of metal, the mechanical strength of the surface of the plastic is improved, the service life of the plastic is prolonged, and the cost is reduced.
The technology of directly forming a three-dimensional circuit on the surface of an injection molding part can realize the electrical interconnection function of a common circuit board, the function of supporting components, the support and protection functions of plastic parts and the like on one device to form a three-dimensional circuit carrier integrating electromechanical functions. The technology can be designed and selected into a proper shape according to needs, can realize multiple functions, can reduce installation levels and reduce the number of components, and is applied to the fields of automobiles, industry, computers, communication and the like at present.
The selective metallization of plastic surfaces is an important link of three-dimensional circuit technology. At present, when a metal layer is selectively formed on the surface of a plastic substrate, common methods include electroplating, vacuum metallization (metal evaporation method), and sputtering, wherein electroplating is the most common method in China, but electroplating has a serious pollution to water and air, and the process is relatively complex, and therefore, the vacuum metallization method and the sputtering method are widely used abroad.
In the prior art, a metal core is formed on the surface of a plastic substrate as a catalytic active center for chemical plating, and then the chemical plating is carried out. Specifically, in the preparation process of the plastic base material, the chemical plating catalyst and the plastic component are directly prepared into the plastic base material in an injection molding mode, so that the chemical plating catalyst is preset in the plastic base material, before chemical plating is carried out, the plastic component in a selected area of the surface of the plastic base material is removed by adopting a method such as laser etching, so that the chemical plating catalyst is exposed in the area, and then chemical plating is carried out on the exposed area, so that a metal layer is formed on the surface of the insulating plastic base material.
The electroless plating catalysts used at present are essentially inorganic compound particles. For example, US2004/0241422a1 discloses adding powders of spinel-structured inorganic compounds containing elements such as copper, nickel, cobalt, chromium, iron, etc. to a polymer matrix, followed by activation with ultraviolet (248 nm, 308nm, and 355nm) and infrared (1064 nm and 10600nm) lasers.
Patent publication No. CN107326414A discloses a chromium-free metallization method for plastic substrates, which comprises the steps of pretreating the plastic substrates, carrying out physical vapor deposition metallization on the plastic substrates, carrying out physical vapor deposition plasma cleaning, plating a bonding layer and a surface layer, directly plating the plastic substrates with a plating layer, carrying out corresponding electroplating process treatment and the like. However, the process has serious environmental pollution, uneven electroplating, and the condition of plating missing or plating failure exists.
In conclusion, the prior art generally has the technical defects of uneven coating, uneven electroplating, plating omission, serious pollution and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a chromium-free metallization method for a plastic substrate. According to the plastic substrate prepared by the chromium-free metallization method, the metal layer has good adhesive force, the functions of quickly dissipating heat and keeping the temperature of the conductive metal layer close to constant can be realized in practical application, the surface treatment process is simple, and the discharge of waste water is greatly reduced.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for the chromium-free metallization of a plastic substrate specifically comprises the following steps:
s1, will carry MgAl2O4And ZnAl2O4Uniformly mixing the granular plastic composition and performing extrusion forming to obtain a plastic sample;
s2, carrying out surface treatment on the plastic sample prepared in the step S1 to obtain a surface-treated plastic sample;
s3, surface-treated plastic prepared in the step S2Irradiating the surface-treated plastic sample with energy beam to gasify and strip the surface to expose MgAl2O4And ZnAl2O4Component particles;
s4, performing direct current sputtering metallization on the irradiated plastic sample in the step S3;
s5, electroplating the sputtered and metallized plastic sample prepared in the step S4 to obtain the product.
Further, the method for the chromium-free metallization of the plastic substrate comprises the step S1 of MgAl2O4And ZnAl2O4The particle size of the particles is 5-10 μm.
Further, the method for the chromium-free metallization of the plastic substrate comprises the step S1 of MgAl2O4And ZnAl2O4The addition amount of the particles is 10-20% of the mass of the plastic component.
Further, the method for the chrome-free metallization of the plastic substrate comprises one or more of wiping, sanding and cleaning processes in the step S2.
Furthermore, in the step S3, the energy beam is laser with a wavelength of 50-100nm, a scanning speed of 300-500mm/S, a step length of 3-9 μm, a frequency of 30-40kHz, a power of 3-4kw, and a filling distance of 10-50 μm.
Further, the working air pressure of the direct current sputtering metallization in the step S4 of the method for the chromium-free metallization of the plastic substrate is 10Pa, the sputtering voltage is 1000V, and the target current density is 0.5mA/cm2The film deposition rate is lower than 0.1 μm/min.
Further, in the method for non-chrome metallization of a plastic substrate, in step S4, the sputtering target for direct current sputtering metallization is one of copper, silver and nickel.
Further, the method for the chrome-free metallization of the plastic substrate comprises the steps of electroplating copper, electroplating silver, electroplating nickel and the like in step S5; the formula of the electrolytic copper plating comprises: 240g/L of copper sulfate 160-The temperature of the electroplating solution is 20-30 ℃, and the cathode current density is 1.5-6A/dm2Electroplating for 5-10 min; the formula of the electrosilvering is as follows: 35-45g/L of silver nitrate, 30-50g/L, SF-950A of potassium carbonate, 180 of complexing agent, 220mL/L, SF-950B of stabilizer, 80-120mL/L, SF-950C of brightener, 40-80mL/L of electroplating solution, 25-35 ℃ of electroplating solution, and 0.2-2A/dm of cathode current density2Electroplating for 5-10 min; the formula of the electroplated nickel is as follows: 300g/L of nickel sulfate 250-5 g/L, 45-55g/L of nickel chloride, 40-50g/L, SF-268 of boric acid and 0.4-0.6mL/L, SF-268 of nickel main polishing agent and 8-12mL/L, SF-268 of nickel softening agent and 1-3mL/L of wetting agent for rack plating, wherein the temperature of electroplating solution is 50-60 ℃, and the cathode current density is 1-8A/dm2The electroplating time is 5-10 min.
Compared with the prior art, the method for the chromium-free metallization of the plastic substrate has the following advantages:
(1) the method for the chromium-free metallization of the plastic base material comprises two parts of sputtering metallization and electroplating, wherein a layer of compact and uniform metal film is formed on the surface of the plastic base material in the sputtering metallization process, the thickness of the sputtering film is increased in the electroplating process, and the flatness of the plated film is adjusted, so that the film formed on the surface of the plastic base material is more uniform and flat;
(2) the method for the chromium-free metallization of the plastic base material provided by the invention adds MgAl into the plastic base material2O4And ZnAl2O4The particles are fine and are uniformly dispersed, the specific surface area of the surface of the plastic base material can be increased after the laser energy beam is irradiated, the adhesion capacity of the sputtering film and the surface of the plastic base material is increased, the prepared plastic product is tightly combined with the film layer, and the effects of quickly dissipating heat and keeping the temperature of the conductive metal layer close to constant can be realized in practical application;
(3) the plastic substrate surface treatment process in the plastic substrate chromium-free metallization method provided by the invention is simple, the waste water discharge amount is less, and the method is energy-saving and environment-friendly.
Detailed Description
The present invention will be further described below by way of specific embodiments, but the present invention is not limited to only the following examples. Various modifications can be made by those skilled in the art based on the basic idea of the invention, but it is within the scope of the invention as long as it does not depart from the basic idea of the invention.
The invention provides a method for chrome-free metallization of a plastic substrate, wherein the plastic substrate comprises a plastic substrate component and an inorganic component, wherein the inorganic component is MgAl2O4And ZnAl2O4And (3) granules.
According to the plastic product provided by the invention, the content of the inorganic component particles is not particularly required, and the conventional amount of the electroless plating catalyst in the field can be referred. For example, the inorganic component content is 10-20% by mass of the plastic component.
According to the plastic product provided by the invention, the particle size of the inorganic component particles can be properly selected according to specific application occasions. The particle size of the inorganic component in this embodiment is 5 to 10 μm. The particle size is an average particle size determined by a liquid phase method using a laser particle sizer.
The base resin may be a thermosetting resin or a thermoplastic resin.
In this embodiment, an ASTMB 368-098H test was conducted in accordance with GBT12967.3-2008 "method for detecting anodic oxide film of aluminum and aluminum alloy", and an ASTM B604-91 test was conducted in accordance with Standard Specification for Decorotive Electroplatable coatings of Copper Plus Nickel Plus Chromium on Plastics "in the United states of America.
Example 1 a method for the chromium-free metallization of a plastic substrate
The method for the chromium-free metallization of the plastic substrate adopted in the embodiment is specifically implemented as follows:
s1, will carry MgAl2O4And ZnAl2O4Uniformly mixing the granular plastic composition and performing extrusion forming to obtain a plastic sample; wherein, MgAl2O4And ZnAl2O4The particle size of the particles is 5 mu m, and the content of the particles is 10 percent of the mass of the plastic component;
s2, performing surface treatment on the plastic sample prepared in the step S1, wherein the surface treatment comprises wiping and sanding processes, and obtaining the plastic sample after the surface treatment;
s3, irradiating the surface-treated plastic sample obtained in the step S2 with an energy beam to gasify and peel the surface of the plastic sample to expose MgAl2O4And ZnAl2O4Component particles: the energy beam is laser, the wavelength is 50nm, the scanning speed is 300mm/s, the step length is 3 mu m, the frequency is 30kHz, the power is 3kw, and the filling space is 10mu m;
s4, performing direct current sputtering metallization on the irradiated plastic sample in the step S3: the working air pressure of the direct current sputtering metallization is 10Pa, the sputtering voltage is 1000V, and the target current density is 0.5mA/cm2The film deposition rate is 0.1 mu m/min;
s5, carrying out copper electroplating on the plastic sample subjected to sputtering metallization prepared in the step S4: 180g/L of copper sulfate, 80mg/L of copper chloride, 80g/L, SF-910MU of copper sulfate, 6mL/L, SF-910A of copper acid open-tank agent, 0.5mL/L, SF-910B of copper acid brightener, 0.3mL/L of copper acid brightener, 20 ℃ of electroplating solution temperature and 4/dm of cathode current density2The plating time was 5 min.
The appearance of the product after electroplating is not different from that of the conventional ABS electroplated product, and can pass the test of ASTM B368-098H and the test of ASTM B604-91.
Example 2a method for chromium-free metallization of a plastic substrate
The method for the chromium-free metallization of the plastic substrate adopted in the embodiment is specifically implemented as follows:
s1, will carry MgAl2O4And ZnAl2O4Uniformly mixing the granular plastic composition and performing extrusion forming to obtain a plastic sample; wherein, MgAl2O4And ZnAl2O4The particle size of the particles is 7 mu m, and the content of the particles is 14 percent of the mass of the plastic component;
s2, carrying out surface treatment on the plastic sample prepared in the step S1, wherein the surface treatment comprises wiping and cleaning processes, and obtaining the plastic sample after surface treatment;
s3, irradiating the surface-treated plastic sample obtained in the step S2 with an energy beam to gasify and peel the surface of the plastic sample to expose MgAl2O4And ZnAl2O4Component particles: the energy beam is laser, the wavelength is 70nm, the scanning speed is 350mm/s, the step length is 5 mu m, the frequency is 34kHz, the power is 3.4kw, and the filling space is 20 mu m;
s4, performing direct current sputtering metallization on the irradiated plastic sample in the step S3: the working air pressure of the direct current sputtering metallization is 10Pa, the sputtering voltage is 1000V, and the target current density is 0.5mA/cm2The film deposition rate is lower than 0.1 mu m/min;
s5, carrying out silver electroplating on the plastic sample subjected to sputtering metallization prepared in the step S4: the formula is as follows: 40g/L of silver nitrate and 40g/L, SF-950A of potassium carbonate, 200mL/L, SF-950B of complexing agent, 100mL/L, SF-950C of stabilizing agent, 50mL/L of brightening agent, 28 ℃ of electroplating solution and 0.5A/dm of cathode current density2The plating time was 5 min.
The appearance of the product after electroplating is not different from that of the conventional ABS electroplated product, and can pass the test of ASTM B368-098H and the test of ASTM B604-91.
Example 3a method for chromium-free metallization of a plastic substrate
The method for the chromium-free metallization of the plastic substrate adopted in the embodiment is specifically implemented as follows:
s1, will carry MgAl2O4And ZnAl2O4Uniformly mixing the granular plastic composition and performing extrusion forming to obtain a plastic sample; wherein, MgAl2O4And ZnAl2O4The particle size of the particles is 9 μm, and the content of the particles is 18 percent of the mass of the plastic component;
s2, performing surface treatment on the plastic sample prepared in the step S1, wherein the surface treatment comprises wiping, sanding and cleaning processes to obtain the plastic sample after surface treatment;
s3, irradiating the surface-treated plastic sample obtained in the step S2 with an energy beam to gasify and peel the surface of the plastic sample to expose MgAl2O4And ZnAl2O4Component particles: the energy beam is laser, the wavelength is 90nm, the scanning speed is 450mm/s, the step length is 7 mu m, the frequency is 38kHz, the power is 3.8kw, and the filling space is 40 mu m;
s4, the step S3 is executedAnd (3) performing direct-current sputtering metallization on the shot plastic sample: the working air pressure of the direct current sputtering metallization is 10Pa, the sputtering voltage is 1000V, and the target current density is 0.5mA/cm2The film deposition rate is lower than 0.1 mu m/min;
s5, performing nickel electroplating on the plastic sample subjected to sputtering metallization prepared in the step S4, wherein the formula of the nickel electroplating is as follows: 250g/L of nickel sulfate, 50g/L of nickel chloride, 0.5mL/L, SF-268 of nickel main plating agent of boric acid, 45g/L, SF-268 of nickel plating main polishing agent, 10mL/L, SF-268 of nickel plating softening agent, and 2.0mL/L of nickel plating wetting agent, wherein the temperature of electroplating solution is 55 ℃, and the cathode current density is 4A/dm2The electroplating time is 8 min.
The appearance of the product after electroplating is not different from that of the conventional ABS electroplated product, and can pass the test of ASTM B368-098H and the test of ASTM B604-91.
Example 4a method for chromium-free metallization of a plastic substrate
The method for the chromium-free metallization of the plastic substrate adopted in the embodiment is specifically implemented as follows:
s1, will carry MgAl2O4And ZnAl2O4Uniformly mixing the granular plastic composition and performing extrusion forming to obtain a plastic sample; wherein, MgAl2O4And ZnAl2O4The particle size of the particles is 10mu m, and the content of the particles is 20 percent of the mass of the plastic component;
s2, performing surface treatment on the plastic sample prepared in the step S1, wherein the surface treatment comprises wiping, sanding and cleaning processes to obtain the plastic sample after surface treatment;
s3, irradiating the surface-treated plastic sample obtained in the step S2 with an energy beam to gasify and peel the surface of the plastic sample to expose MgAl2O4And ZnAl2O4Component particles: the energy beam is laser with the wavelength of 100nm, the scanning speed of 500mm/s, the step length of 9 microns, the frequency of 40kHz, the power of 4kw and the filling interval of 50 microns;
s4, performing direct current sputtering metallization on the irradiated plastic sample in the step S3: the working air pressure of the direct current sputtering metallization is 10Pa, the sputtering voltage is 1000V, and the target current density is 0.5mA/cm2The film deposition rate is lower than 0.1 mu m/min;
s5, carrying out copper electroplating on the plastic sample subjected to sputtering metallization prepared in the step S4, wherein the formula is as follows: 200g/L of copper sulfate, 80mg/L of copper chloride, 70g/L, SF-910MU copper acid open-cylinder agent 8mL/L, SF-910A copper acid leveling agent 0.5mL/L, SF-910B copper acid brightening agent 0.4mL/L, electroplating solution temperature of 25 ℃, and cathode current density of 3A/dm2The plating time was 7 min.
The appearance of the product after electroplating is not different from that of the conventional ABS electroplated product, and can pass the test of ASTM B368-098H and the test of ASTM B604-91.
Comparative example, method for the chromium-free metallization of a plastic substrate
The method for the chromium-free metallization of the plastic substrate adopted by the comparative example is specifically implemented as follows:
s1, uniformly mixing the plastic composition and carrying out extrusion molding to obtain a plastic sample;
s2, performing surface treatment on the plastic sample prepared in the step S1, wherein the surface treatment comprises wiping, sanding and cleaning processes to obtain the plastic sample after surface treatment;
s3, irradiating the surface-treated plastic sample prepared in the step S2 with an energy beam: the energy beam is laser with the wavelength of 100nm, the scanning speed of 500mm/s, the step length of 9 microns, the frequency of 40kHz, the power of 4kw and the filling interval of 50 microns;
s4, performing direct current sputtering metallization on the irradiated plastic sample in the step S3: the working air pressure of the direct current sputtering metallization is 10Pa, the sputtering voltage is 1000V, and the target current density is 0.5mA/cm2The film deposition rate is lower than 0.1 mu m/min;
s5, carrying out copper electroplating on the plastic sample subjected to sputtering metallization prepared in the step S4, wherein the formula is as follows: 200g/L of copper sulfate, 80mg/L of copper chloride, 70g/L, SF-910MU copper acid open-cylinder agent 8mL/L, SF-910A copper acid leveling agent 0.5mL/L, SF-910B copper acid brightening agent 0.4mL/L, electroplating solution temperature of 25 ℃, and cathode current density of 3A/dm2The plating time was 7 min.
The comparison example differs from example 4 in that the comparison example comprises a plastic combinationThe product is not added with MgAl2O4And ZnAl2O4And (3) granules.
The appearance of the electroplated product is not bright and flat compared with the appearance of the conventional ABS electroplated product, and the product cannot pass the ASTMB 368-098H experiment and the ASTM B604-91 experiment.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art will recognize that changes may be made to the embodiments described above without departing from the spirit and scope of the invention. Therefore, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the technical spirit of the present invention are covered by the claims of the present invention.
Claims (8)
1. A method for chrome-free metallization of a plastic substrate, comprising the steps of:
s1, will carry MgAl2O4And ZnAl2O4Uniformly mixing the granular plastic composition and performing extrusion forming to obtain a plastic sample;
s2, carrying out surface treatment on the plastic sample prepared in the step S1 to obtain a surface-treated plastic sample;
s3, irradiating the surface-treated plastic sample obtained in the step S2 with an energy beam to gasify and peel the surface of the plastic sample to expose MgAl2O4And ZnAl2O4Component particles;
s4, performing direct current sputtering metallization on the irradiated plastic sample in the step S3;
s5, electroplating the sputtered and metallized plastic sample prepared in the step S4 to obtain the product.
2. The method according to claim 1, characterized in that the MgAl is used in step S1 for chrome-free metallization of plastic substrates2O4And ZnAl2O4The particle size of the particles is 5-10 μm.
3. Plastic base according to claim 1The method for chromium-free metallization of a material is characterized in that MgAl is used in step S12O4And ZnAl2O4The addition amount of the particles is 10-20% of the mass of the plastic component.
4. The method of claim 1, wherein the surface treatment in step S2 comprises one or more of wiping, sanding, and cleaning.
5. The method as claimed in claim 1, wherein the energy beam in step S3 is laser with a wavelength of 50-100nm, a scanning speed of 300-500mm/S, a step size of 3-9 μm, a frequency of 30-40kHz, a power of 3-4kw, and a filling pitch of 10-50 μm.
6. The method according to claim 1, wherein the DC sputtering metallization in step S4 has a working gas pressure of 10Pa, a sputtering voltage of 1000V, and a target current density of 0.5mA/cm2The film deposition rate is lower than 0.1 μm/min.
7. The method according to claim 1, wherein the sputtering target for direct current sputtering metallization in step S4 is one of copper, silver and nickel.
8. The method of claim 1, wherein the electroplating in step S5 is a copper electroplating process, a silver electroplating process, a nickel electroplating process, or the like; the formula of the electrolytic copper plating comprises: 240g/L of copper sulfate 160-2Electroplating for 5-10 min; the formula of the electrosilvering is as follows: 35-45g/L silver nitrate, 30-50g/L, SF-950A potassium carbonate, 180 complexing agent and 220mL/L, SF-950B stabilizer, 80-120mL/L, SF-950C light40-80mL/L brightener, 25-35 ℃ electroplating solution temperature and 0.2-2A/dm cathode current density2Electroplating for 5-10 min; the formula of the electroplated nickel is as follows: 300g/L of nickel sulfate 250-5 g/L, 45-55g/L of nickel chloride, 40-50g/L, SF-268 of boric acid and 0.4-0.6mL/L, SF-268 of nickel main polishing agent and 8-12mL/L, SF-268 of nickel softening agent and 1-3mL/L of wetting agent for rack plating, wherein the temperature of electroplating solution is 50-60 ℃, and the cathode current density is 1-8A/dm2The electroplating time is 5-10 min.
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