CN112552544B - Surface metallized polymer material and preparation method and application thereof - Google Patents

Surface metallized polymer material and preparation method and application thereof Download PDF

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CN112552544B
CN112552544B CN202011310179.2A CN202011310179A CN112552544B CN 112552544 B CN112552544 B CN 112552544B CN 202011310179 A CN202011310179 A CN 202011310179A CN 112552544 B CN112552544 B CN 112552544B
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polymer material
high polymer
metal foil
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electroplating
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CN112552544A (en
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邢清松
陈安伏
秦国锋
刘俊杰
古杭
张艳梅
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The application belongs to the technical field of surface metallization of high polymer materials. The application provides a surface metallization high polymer material, and a preparation method and application thereof. The metal foil with the microstructured coating on the surface is obtained by polishing, prepressing and electroplating the metal foil in sequence, then the metal foil is bonded with a high polymer material for forming, and the microstructured coating is transferred to the surface of the high polymer material, so that the surface metallized high polymer material with the microscale pattern structure is obtained. The preparation method realizes micro-scale structuring and patterning of the metal on the surface of the high polymer material and realizes the functions of decoration and electric conduction of the surface of the high polymer material. The preparation method has the advantages that the process flow is simple and quick, the metal foil can be recycled, the method is suitable for the metallization of the surfaces of various high polymer materials, and the complex physical or chemical pretreatment of the high polymer materials is not needed.

Description

Surface metallized polymer material and preparation method and application thereof
Technical Field
The application belongs to the technical field of surface metallization of high polymer materials, and particularly relates to a surface-metallized high polymer material, and a preparation method and application thereof.
Background
The polymer material product with surface metallization forms metal texture on the surface of the base material to improve the decoration performance, simultaneously reduces the quality of the product effectively, improves the surface performance of the polymer base material, such as wear resistance, heat resistance, weather resistance, corrosion resistance and the like, improves the mechanical performance of the product, and ensures that the product obtains the conductive performance of metal. The prior art for realizing the metallization of the polymer surface is mainly divided into a dry coating and a wet coating.
Wet plating refers to a plating method in which a piece to be plated is immersed in a solution to deposit a metal material on a substrate surface, wherein electroless plating and electroplating are the most typical and more mature and widely used metallization methods. Because the high molecular material has the characteristics of large crystallinity, small polarity, low surface energy and the like, the adhesive force between the plating layer and the base material can be influenced, and most of the high molecular material is a non-conductive insulator, the chemical plating and electroplating methods need to strictly control the deposition rate of the plating layer, the stability of plating solution, the technological parameters of an electroplated conductive system and the like, so that a metal plating layer with compact and uniform structure and good bonding force with the base material can be formed, and the method is difficult to be applied to the high molecular material with difficult surface roughening, and the continuous automatic production of electroplated parts is difficult to realize.
The dry coating is mainly divided into two main categories, namely vacuum coating and metal transfer coating. The common methods for vacuum coating include vacuum evaporation coating, magnetron sputtering coating and ion plating. The application of the vacuum evaporation coating technology is limited by the melting point of the coated metal material, and the energy consumption is high; unstable plasmas are easy to generate in magnetron sputtering coating, and the quality of products is influenced; the ion plating needs a low-temperature film forming environment, when charged ions bombard the surface of a workpiece, gas molecules can be adsorbed on the surface of the film, and positive gas ions can enter the film, so that the gas content in the deposited film is high. The metal transfer method is difficult to realize surface lamination of complex structures at present, and the application field is limited.
Disclosure of Invention
In view of the above, the present application provides a surface-metallized polymer material, and a preparation method and application thereof, so as to obtain a surface-metallized polymer material with a micro-scale structure and patterning.
The specific technical scheme of the application is as follows:
the first aspect of the present application provides a method for preparing a surface-metallized polymer material, which includes the following steps:
s1: polishing, pre-embossing and electroplating the metal foil in sequence to obtain a treated metal foil;
s2: and (3) attaching and fixing the treated plating surface of the metal foil and the high polymer material in a mold for molding, and tearing off the metal foil to obtain the surface metallized high polymer material.
In the application, the metal foil with the microstructured coating on the surface is obtained by sequentially polishing, pre-embossing and electroplating the metal foil, and then is bonded with the high polymer material to form, and the microstructured coating is transferred to the surface of the high polymer material to obtain the surface metallized high polymer material with the microscale pattern structure. The preparation method solves the problem that the surface cannot form complex micro-morphology in the existing high polymer material surface metallization method, realizes micro-scale structuring and patterning of high polymer material surface metal, and realizes the functions of decoration and electric conduction of the high polymer material surface. Meanwhile, the preparation method has simple and quick process flow, the metal foil can be repeatedly utilized, the method is suitable for the metallization of the surfaces of various high polymer materials, and complex physical or chemical pretreatment of the high polymer materials is not needed.
Preferably, the metal foil is aluminum foil;
the high polymer material is selected from Polydimethylsiloxane (PDMS), polypropylene (PP) or Polycarbonate (PC);
the plating layer is selected from copper plating, nickel plating or silver plating.
In the application, the metal aluminum is used as a base material for metallization transfer of the surface of the high polymer material, and is more beneficial to realizing transfer of a coating. Because aluminum has high electron affinity, an oxide film is extremely easy to form on the surface of the aluminum, and the existence of the oxide film can reduce the binding force between a plating layer and a metal foil, so that the plating layer is more easily separated from the surface of the metal foil and transferred to the surface of a high polymer material. In addition, the aluminum has low strength and good plasticity, can be subjected to various mechanical pre-processing, and is easier to realize the micro-structuring and patterning of the surface, so that the micro-structured and patterned plating layer is transferred to the surface of the high polymer material.
Preferably, before the polishing, further:
and sequentially ultrasonically cleaning the metal foil in distilled water, acetone and absolute ethyl alcohol for 5-15 min.
Preferably, the polishing solution is a mixed solution of perchloric acid and ethanol, and the volume ratio of perchloric acid to ethanol is 1 (8-9).
Preferably, the polishing voltage is 20V and the polishing time is 5-10 min. More preferably, the polishing is to put the metal foil as an anode in a polishing solution and the graphite sheet as a cathode, and after polishing, rinse the metal foil with deionized water and dry the metal foil under the protection of inert gas.
Preferably, the pre-embossed template is selected from plain, twill or punched screens. More preferably, the plain mesh screen or the twill mesh screen is a stainless steel screen, and the mesh number of the screen is 10 to 1000 mesh.
Preferably, the pre-embossing conditions are cold pressing under (25-35) MPa, or hot pressing under (150-200) DEG C and (7-10) MPa.
Preferably, the formula of the electroplating solution for electroplating is as follows:
80-160 g/L copper sulfate solution, 0.05-0.1 g/L polyethylene glycol and 0.02-0.08 g/L dilute hydrochloric acid.
Preferably, the temperature of the electroplating is 0-25 ℃ and the current density is 0.03-0.1A/cm 2 The time is 10 min-60 min. More preferably, the plating is performed with a metal foil as a cathode, a copper plate or a graphite sheet as an anode. And after the electroplating is finished, ultrasonically cleaning the coating for 2min by using deionized water under low power, and drying under the protection of inert gas.
In the application, the method for electroplating the coating can balance the binding force between the coating and the metal foil substrate and the morphology of the coating, thereby facilitating the transfer of the coating and maintaining the microstructure and pattern of the coating.
Preferably, the polymer material and the curing agent are mixed in advance according to (10-12): mixing the materials according to the mass ratio of 1;
the high polymer material is polydimethylsiloxane;
the curing agent is SYLGARD184.
Preferably, the die is a circular orifice plate. More preferably, the treated metal foil is fixed by a polyimide tape with high temperature resistance, and the thickness of the die is 2mm and the diameter of the die is 20mm.
Preferably, the molding temperature is 120 ℃ and the molding time is 1h.
Preferably, after said tearing off the metal foil, further:
ultrasonic cleaning, repeating the electroplating coating in the step S1.
The second aspect of the application provides a surface metallization polymer material, which is prepared by the preparation method, wherein the surface metallization has a micro-scale pattern structure.
A third aspect of the present application provides the use of the surface-metallized polymeric material in an electronic device, biomedical, optical element, biomimetic material or energy storage material.
In the application, the surface metallization treatment is carried out on the high polymer material, the micro-structuring and patterning of the surface are realized, a metal layer with a micro-scale pattern structure is formed on the surface, the surface decoration and the conductive function of the high polymer material are realized, and the high polymer material is expected to be applied to the fields of bionics, electricity, magnetism or energy storage materials and the like. The surface metallization polymer material can also be applied to the fields of electronic devices, biomedical treatment, optics and the like. For example, in the flexible sensor aspect, the metal surface with the micro-scale structure can improve the sensitivity of the sensor and increase the pressure response range; in the aspect of biological medical treatment, the metal surface of the micro-scale structure is modified to realize a hydrophobic effect, so that the antibacterial function of the surface is enhanced.
In summary, the application provides a surface metallization polymer material, a preparation method and an application thereof, wherein a metal foil with a microstructured coating on the surface is obtained by sequentially polishing, pre-embossing and electroplating the metal foil, and then the metal foil is bonded with the polymer material for forming, and the microstructured coating is transferred to the surface of the polymer material to obtain the surface metallization polymer material with a microscale graphic structure. The preparation method solves the problem that the surface cannot form complex micro morphology in the existing high polymer material surface metallization method, realizes micro-scale structuring and patterning of high polymer material surface metal, realizes the functions of decoration and conduction of the high polymer material surface, and is expected to be applied to electronic devices, biomedical, optical elements, bionic materials or energy storage materials. Meanwhile, the preparation method has simple and quick process flow, the metal foil can be repeatedly utilized, the method is suitable for the metallization of the surfaces of various high polymer materials, and complex physical or chemical pretreatment of the high polymer materials is not needed.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing a surface-metallized polymer material provided by the present application;
FIG. 2 is an optical micrograph of a surface structured aluminum foil obtained in step II of example 1 of the present application;
FIG. 3 is an optical micrograph of a surface-metallized PDMS surface obtained in example 2 of the present application;
FIG. 4 is an optical micrograph of the surface of the product 1 obtained in comparative example 1 of the present application;
FIG. 5 is an optical micrograph of the surface of product 2 obtained in comparative example 2 of the present application;
FIG. 6 is an optical micrograph of the surface of the product 3 obtained in comparative example 3 of the present application;
wherein: 1. a metal foil; 2. a surface structured metal foil; 3. plating; 4. a polymer material; 5. a surface-metallized polymer material; 6. a surface-metallized polymeric material having a microscale pattern.
Detailed Description
For the purposes of making the objects, features, and advantages of the present application more apparent and understandable, the technical solutions in the embodiments of the present application are clearly and completely described, and it is apparent that the embodiments described below are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Example 1
Step I, sequentially placing the aluminum foil in distilled water, acetone and absolute ethyl alcohol, and respectively ultrasonically cleaning for 15min to remove oil stains adhered to the surface; and (3) placing the aluminum foil serving as an anode in a polishing solution (a mixed solution of perchloric acid and ethanol in a volume ratio of 1:9), polishing at 0 ℃ and a constant pressure of 20V for 5min by using a graphite sheet as a cathode, and finally washing with deionized water and drying under the protection of nitrogen to obtain the aluminum foil with a smooth mirror surface.
And II, pre-embossing the aluminum foil obtained in the step I by using a 500-mesh plain stainless steel screen, flatly placing the clean stainless steel screen on the surface of the aluminum foil, cold pressing under 30MPa, and maintaining the pressure for 1min. And after the imprinting is finished, uncovering the stainless steel screen to obtain the aluminum foil with the structured surface.
Step III, using 100g/L copper sulfate solution, adding 0.05g/L polyethylene glycol and 0.02g/L dilute hydrochloric acid as leveling agents, adjusting the pH value to 2 by using dilute sulfuric acid to obtain plating solution for electroplating, wherein the temperature of the plating solution is 5 ℃, adopting a direct current power supply to carry out electroplating treatment, using a copper plate as an anode, using an aluminum foil as a cathode, and using the current density of 0.04A/cm 2 The electroplating time is 20min, and a stirrer is used for slowly stirring the plating solution in the electroplating process. And after the deposition is finished, the aluminum foil with the metal deposited on the surface is washed clean by using deionized water, residual plating solution on the surface is removed, and then the aluminum foil is dried under the protection of nitrogen.
And IV, fixing the aluminum foil with the surface subjected to metal deposition on a metal round hole plate with the thickness of 2mm and the diameter of 20mm by using a high-temperature-resistant adhesive tape, and taking the plating layer surface as a contact surface with a high polymer material. PDMS and SYLGARD184 curing agent are mixed and stirred uniformly according to the proportion of 10:1, poured into a pore plate, vacuumized and placed for 30min, bubbles are removed, and then curing is carried out at 120 ℃ for 1h. After curing was completed, the aluminum foil was torn off to obtain surface-metallized PDMS.
As shown in fig. 2, the optical micrograph of the aluminum foil with the structured surface obtained in step II of example 1 of the present application has a plain weave structure on the surface of the pre-embossed aluminum foil, which lays a foundation for forming a micro-scale pattern structure with a metallized surface.
Example 2
Step I, sequentially placing the aluminum foil in distilled water, acetone and absolute ethyl alcohol, and respectively ultrasonically cleaning for 15min to remove oil stains adhered to the surface; and (3) placing the aluminum foil serving as an anode in a polishing solution (a mixed solution of perchloric acid and ethanol in a volume ratio of 1:9), polishing the graphite sheet serving as a cathode at a constant pressure of 20V at 0 ℃ for 5min, and finally washing with deionized water and drying with nitrogen to obtain the aluminum foil with a smooth mirror surface.
And II, pre-embossing the aluminum foil obtained in the step I by using a 3000-mesh diagonal stainless steel screen, flatly placing the clean stainless steel screen on the surface of polished aluminum, cold pressing under 30MPa, and maintaining the pressure for 1min. And after the imprinting is finished, uncovering the stainless steel screen to obtain the aluminum foil with the structured surface.
Step III, using 100g/L copper sulfate solution, adding 0.05g/L polyethylene glycol and 0.02g/L dilute hydrochloric acid as leveling agents, adjusting the pH value to 2 by using dilute sulfuric acid, wherein the temperature of the plating solution is 5 ℃, adopting a direct current power supply, a copper plate as an anode, an aluminum foil as a cathode and the current density is 0.04A/cm 2 The electroplating time is 20min, and a stirrer is used for slowly stirring the plating solution in the electroplating process. And after the deposition is finished, the surface is washed clean by deionized water, residual plating solution on the surface is removed, and then the surface is dried by nitrogen.
And IV, fixing the aluminum foil with the surface subjected to metal deposition on a metal round hole plate with the thickness of 2mm and the diameter of 20mm by using a high-temperature-resistant adhesive tape, and taking the plating layer surface as a contact surface with a high polymer material. PDMS and SYLGARD184 curing agent are mixed and stirred uniformly according to the proportion of 10:1, poured into a pore plate, vacuumized and placed for 30min, bubbles are removed, and then curing is carried out at 120 ℃ for 1h. After curing was completed, the aluminum foil was torn off to obtain surface-metallized PDMS.
The optical micrograph of the surface-metallized PDMS surface obtained in example 2 of the present application is shown in fig. 3, and the surface of the prepared surface-metallized PDMS has a twill structure, so as to implement micro-scale structuring and patterning of the surface metal of the polymer material.
Comparative example 1
Step I, sequentially placing the aluminum foil in distilled water, acetone and absolute ethyl alcohol, and respectively ultrasonically cleaning for 15min to remove oil stains adhered to the surface; and (3) placing the aluminum foil serving as an anode in a polishing solution (a mixed solution of perchloric acid and ethanol in a volume ratio of 1:9), polishing the graphite sheet serving as a cathode at a constant pressure of 20V at 0 ℃ for 5min, and finally washing with deionized water and drying under the protection of nitrogen to obtain the aluminum foil with a smooth mirror surface.
Step II, using 100g/L copper sulfate solution, using dilute sulfuric acid to adjust the pH value to 2, using a direct current power supply to make the plating solution temperature be 0 ℃, using a copper plate as an anode, using an aluminum foil as a cathode, and making the current density be 0.03A/cm 2 The electroplating time is 10min, and a stirrer is used for slowly stirring the plating solution in the electroplating process. And after the deposition is finished, the surface is washed clean by deionized water, residual plating solution on the surface is removed, and then the surface is dried under the protection of nitrogen.
And III, fixing the aluminum foil with the surface subjected to metal deposition on a metal round hole plate with the thickness of 2mm and the diameter of 20mm by using a high-temperature-resistant adhesive tape, and taking the plating layer surface as a contact surface with a high polymer material. PDMS and SYLGARD184 curing agent are mixed and stirred uniformly according to the proportion of 10:1, poured into a pore plate, vacuumized and placed for 30min, bubbles are removed, and then curing is carried out at 120 ℃ for 1h. After completion of the curing, the aluminum foil was peeled off to obtain product 1.
The optical microscope photograph of the surface of the product 1 obtained in comparative example 1 of the present application is shown in FIG. 4. As can be seen in fig. 4, product 1 is a flexible PDMS with a metallic luster on the surface, which is not micro-scale structured and patterned due to the absence of a pre-embossing step. In the comparative example, no leveling agent is added in the plating solution, the plating time is short, the plating solution temperature is low, the obtained plating layer is discontinuous, each metal cluster is presented, and the surface does not have conductive property.
Comparative example 2
Step I, sequentially placing the aluminum foil in distilled water, acetone and absolute ethyl alcohol, and respectively ultrasonically cleaning for 15min to remove oil stains adhered to the surface; and (3) placing the aluminum foil serving as an anode in a polishing solution (a mixed solution of perchloric acid and ethanol in a volume ratio of 1:9), polishing the graphite sheet serving as a cathode at a constant pressure of 20V at 0 ℃ for 5min, and finally washing with deionized water and drying under the protection of nitrogen to obtain the aluminum foil with a smooth mirror surface.
Step II, using 100g/L copper sulfate solution, adding polyethylene glycol, using a small amount of dilute hydrochloric acid as a leveling agent, using dilute sulfuric acid to adjust the PH value to 2, using a direct current power supply to make the plating solution temperature 15 ℃, using a copper plate as an anode, using an aluminum foil as a cathode, and making the current density 0.08A/cm 2 The electroplating time is 40min, and a stirrer is used for slowly stirring the plating solution in the electroplating process. And after the deposition is finished, the surface is washed clean by deionized water, residual plating solution on the surface is removed, and then the surface is dried under the protection of nitrogen.
And III, fixing the aluminum foil with the surface subjected to metal deposition on a metal round hole plate with the thickness of 2mm and the diameter of 20mm by using a high-temperature-resistant adhesive tape, and taking the plating layer surface as a contact surface with a high polymer material. PDMS and SYLGARD184 curing agent are mixed and stirred uniformly according to the proportion of 10:1, poured into a pore plate, vacuumized and placed for 30min, bubbles are removed, and then curing is carried out at 120 ℃ for 1h. After curing is completed, the aluminum foil is torn off to give product 2.
The optical microscope photograph of the surface of the product 2 obtained in comparative example 2 of the present application is shown in FIG. 5. As can be seen from fig. 5, under the conditions of adding the leveler, prolonging the electroplating time, increasing the electroplating current and increasing the temperature of the plating solution, the surface of the finally obtained product 2 has a thicker and conductive copper plating layer, but no micro-scale structuring and patterning is formed yet. In the comparative example, due to the factors of overlong electroplating time, higher temperature, overlarge current and the like in the electroplating process, the plating layer is deposited too quickly, so that stress is generated, cracking and even falling off of the plating layer are easy to cause, the plating layer is difficult to transfer to the surface of a high polymer material, and the subsequent process is difficult to carry out.
Comparative example 3
Step I, sequentially placing the aluminum foil in distilled water, acetone and absolute ethyl alcohol, and respectively ultrasonically cleaning for 15min to remove oil stains adhered to the surface; and (3) placing the aluminum foil serving as an anode in a polishing solution (a mixed solution of perchloric acid and ethanol in a volume ratio of 1:9), polishing the graphite sheet serving as a cathode at a constant pressure of 20V at 0 ℃ for 5min, and finally washing with deionized water and drying with nitrogen to obtain the aluminum foil with a smooth mirror surface.
Step II, using 100g/L copper sulfate solution, adding 0.05g/L polyethylene glycol and 0.02g/L dilute hydrochloric acid as leveling agents, adjusting the pH to 2 by using dilute sulfuric acid, wherein the temperature of the plating solution is 5 ℃, adopting a direct current power supply, a copper plate as an anode, an aluminum foil as a cathode and the current density is 0.04A/cm 2 The electroplating time is 20min, and a stirrer is used for slowly stirring the plating solution in the electroplating process. And after the deposition is finished, the surface is washed clean by deionized water, residual plating solution on the surface is removed, and then the surface is dried under the protection of nitrogen.
And III, fixing the aluminum foil with the surface subjected to metal deposition on a metal round hole plate with the thickness of 2mm and the diameter of 20mm by using a high-temperature-resistant adhesive tape, and taking the plating layer surface as a contact surface with a high polymer material. PDMS and SYLGARD184 curing agent are mixed and stirred uniformly according to the proportion of 10:1, poured into a pore plate, vacuumized and placed for 30min, bubbles are removed, and then curing is carried out at 120 ℃ for 1h. After curing is completed, the aluminum foil is torn off to give product 3.
The optical microscope photograph of the surface of the product 3 obtained in comparative example 3 of the present application is shown in FIG. 6. Fig. 6 shows that the product 3 surface is provided with a copper plating of uniform and moderate thickness and which is electrically conductive, but still not micro-scale structuring and patterning.
In conclusion, by adding the leveling agent into the formula of the plating solution, the temperature of the plating solution is controlled below 10 ℃, and the current density is controlled between 0.03 and 0.06A/cm 2 The electroplating time is controlled between 10min and 30min, and the binding force between the plating layer and the metal foil and the shape of the plating layer can be adjusted to be the optimal state. Meanwhile, the metal foil is mechanically pre-processed, so that the prepared high polymer material with the surface being metallized realizes the micro-structuring and patterning of the surface, thereby realizing the functions of surface decoration and electric conduction, and being applicable to the fields of electronic devices, biological medical treatment, optical elements, bionic materials or energy storage materials and the like.
The above embodiments are merely for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (6)

1. The preparation method of the surface metallized polymer material is characterized by comprising the following steps:
s1: polishing, pre-embossing and electroplating the metal foil in sequence to obtain a treated metal foil;
s2: attaching and fixing the treated plating surface of the metal foil and the high polymer material in a mold for molding, and tearing off the metal foil to obtain a surface metallized high polymer material;
the formula of the electroplating solution for electroplating comprises the following components:
80-160 g/L copper sulfate solution, 0.05-0.1 g/L polyethylene glycol and 0.02-0.08 g/L dilute hydrochloric acid;
the temperature of the electroplating is 0-25 ℃, and the current density is 0.03-0.1A/cm 2 The time is 10 min-60 min;
the metal foil is aluminum foil;
the high polymer material is selected from polydimethylsiloxane, polypropylene or polycarbonate;
the pre-stamping condition is cold pressing under 25-30 MPa, or hot pressing under 7-10 MPa at 150-200 ℃.
2. The preparation method of the polishing liquid according to claim 1, wherein the polishing liquid is a mixed solution of perchloric acid and ethanol, and the volume ratio of perchloric acid to ethanol is 1 (8-9).
3. The method of manufacturing according to claim 1, wherein the pre-embossed template is selected from plain, twill or punched screens.
4. The preparation method of claim 1, wherein the polymer material is pre-mixed with a curing agent in an amount of (10-12): mixing the materials according to the mass ratio of 1;
the high polymer material is polydimethylsiloxane;
the curing agent is SYLGARD184.
5. The surface metallization polymer material is characterized by being prepared by the preparation method according to any one of claims 1-4, wherein the surface metallization has a micro-scale pattern structure.
6. The use of the surface-metallized polymeric material according to claim 5, in electronic devices, optical components, biomimetic materials or energy storage materials.
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