CN110438499B - Non-metallic material surface metallization product and metallization method thereof - Google Patents

Non-metallic material surface metallization product and metallization method thereof Download PDF

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Publication number
CN110438499B
CN110438499B CN201910696684.6A CN201910696684A CN110438499B CN 110438499 B CN110438499 B CN 110438499B CN 201910696684 A CN201910696684 A CN 201910696684A CN 110438499 B CN110438499 B CN 110438499B
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Prior art keywords
metal layer
agent
copper
solution
water
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CN110438499A (en
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曾庆明
孙宇曦
宋亦健
李友
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Guangdong Shuocheng Technology Co ltd
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Guangdong Shuocheng Technology Co ltd
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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
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

Abstract

The invention provides a non-metallic material surface metallization product and a metallization method thereof, wherein the product comprises at least one non-metallic layer and at least one metallic layer; the metal layer is made of a metal material, and the non-metal layer is made of plastic and/or rubber; the method has the advantages of high bonding fastness of the non-metal layer and the metal layer, excellent mechanical property and the like.

Description

Non-metallic material surface metallization product and metallization method thereof
Technical Field
The invention relates to the field of surface metallization of non-metallic materials, in particular to a surface metallization preparation method of plastic and a product.
Background
The metal layer is formed on the surface of the non-metal material, and is widely used in the fields of automobiles, industry, computers, communication and the like as a path for electromagnetic signal conduction.
The method for coating the metal layer on the surface of the non-metal material also comprises a vacuum evaporation method, a magnetron sputtering method and an ion plating method. Chinese patent CN85109145 discloses "a plastic product plated with metal and a manufacturing method thereof", wherein the coating method adopts a magnetron sputtering method. Chinese patent CN1117916 discloses "metallized plastic products", and the coating method is vacuum deposition or vacuum spraying. Chinese patent CN1162654 discloses "thermoplastic metal coating" which is carried out by vapor deposition or sputtering. For low surface energy plastics such as polypropylene, pretreatment (surface dust removal, roughening, activation and grafting) such as chemical treatment, electric spark treatment or low temperature plasma treatment is required before coating. The metal vapor deposition method inevitably causes surface damage. The methods still have the defects of low bonding fastness between the non-metal layer and the metal layer, poor mechanical property and the like.
In view of the above situation, the present invention provides a metalized product on the surface of a non-metallic material and a method for metalizing the same.
Disclosure of Invention
The invention provides in a first aspect a non-metallic material surface metallised article comprising at least one non-metallic layer and at least one metallic layer; the metal layer is made of a metal material, and the nonmetal layer is made of a nonmetal material;
the metal material at least comprises a transition metal; the non-metallic material is plastic and/or rubber.
As an embodiment of the present invention, the transition metal is selected from one or more of chromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, silver, platinum, gold, or mercury.
As an embodiment of the present invention, the transition metal is selected from one or more of nickel, manganese, iron, cobalt, copper, chromium, silver or zinc.
In one embodiment of the present invention, the non-metallic material is plastic.
As an embodiment of the present invention, the non-metallic material is selected from one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polymethacrylate, polyethylene terephthalate, polybutylene terephthalate, and polyurethane.
In one embodiment of the present invention, the non-metal layer is made of a plastic film.
In a second aspect, the present invention provides a method for preparing a metalized article on the surface of the above-mentioned non-metallic material, said method at least comprising the following steps:
metallization is carried out by adopting a sputtering coating mode;
and adopting an electroplating film-plating mode to carry out metallization.
As an embodiment of the present invention, the method includes the steps of:
s01, metallizing the surface of the non-metal layer by a sputtering coating method to form a first metal layer and a second metal layer;
s02, forming a third metal layer on the surface of the second metal layer by adopting a chemical plating mode;
and S03, forming a fourth metal layer on the surface of the third metal layer by adopting an electroplating film plating mode.
In one embodiment of the present invention, the metal material of the third metal layer and the metal material of the fourth metal layer are the same.
In one embodiment of the present invention, the metal material of the third metal layer is copper.
Has the advantages that:
the invention adopts specific deposition technology and process, and the prepared metal layer and the non-metal layer have firm bonding force and have the advantages of light-proof property and the like; meanwhile, the invention realizes the effective deposition of different metals by adjusting the process parameters of the actual deposition technology.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided herein, the definition of the term provided herein controls.
As used herein, a feature that is not limited to a single plural form is also intended to include plural forms of the feature unless the context clearly indicates otherwise. It will also be understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "containing," and/or "containing," when used in this specification denotes a stated composition, step, method, article, or apparatus, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or apparatuses. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The invention provides a non-metallic material surface metallization product, which comprises at least one non-metallic layer and at least one metallic layer; the metal layer is made of a metal material, and the nonmetal layer is made of a nonmetal material.
The metal material at least comprises transition metal, and the non-metal material is plastic and/or plastics.
Metal layer
In the present invention, the metal layer refers to a metal surface formed on the surface of the non-metal layer by sputtering, chemical plating, electroplating, or the like.
As an embodiment of the present invention, the number of the metal layers may be one, and the plating may be performed by any one of sputter plating, electroless plating, and electroplating.
As an embodiment of the present invention, the number of the metal layers may be two, and any two of the sputtering coating, the electroless plating and the electroplating may be used for the respective coating.
As an embodiment of the present invention, the number of the metal layers may be three, and the metal layers are respectively formed by sputtering, electroless plating and electroplating.
As an embodiment of the present invention, the number of the metal layers may be more than three.
Transition metal
Transition metal refers to a series of metal elements in the d region of the periodic table; generally, this region includes a total of ten elements of groups 3 to 12, but does not include the inner transition element of the f-block.
As an embodiment of the present invention, the transition metal is selected from one or more of chromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, silver, platinum, gold, or mercury.
As a preferred mode of the present invention, the filter metal is one or more selected from the group consisting of nickel, manganese, iron, cobalt, copper, chromium, silver and zinc.
In a further preferred embodiment of the present invention, the transition metal is one or more selected from the group consisting of Ni, Co, Cu and Ag.
Non-metal layer
In the present invention, the non-metal layer is composed of a plastic and/or rubber material.
In one embodiment of the present invention, the non-metallic layer is made of plastic.
As an embodiment of the present invention, the plastic is selected from one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polymethacrylate, polyethylene terephthalate, polybutylene terephthalate, or polyurethane.
From the viewpoint of improving the bonding force between the non-metal layer and the metal layer, the plastic is selected from one of polypropylene, polyethylene and polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate and polyurethane.
From the perspective of reducing the light transmittance of the metalized product, the non-metal layer is made of a plastic film, and the thickness of the plastic film is 2-1000 mu m; more preferably 2 to 100 μm.
In a second aspect, the present invention provides a method for preparing a metalized article on the surface of the above-mentioned non-metallic material, said method at least comprising the following steps:
metallization is carried out by adopting a sputtering coating mode;
and adopting an electroplating film-plating mode to carry out metallization.
As an embodiment of the invention, the metallization method of the product with the metalized surface of the non-metallic material comprises the following steps:
s01, metallizing the surface of the non-metal layer by a sputtering coating method to form a first metal layer and a second metal layer;
s02, forming a third metal layer on the surface of the second metal layer by adopting a chemical plating mode;
and S03, forming a fourth metal layer on the surface of the third metal layer by adopting an electroplating film plating mode.
Sputter coating
Common sputtering coating methods mainly include direct current sputtering, radio frequency sputtering, magnetron sputtering, and reactive sputtering.
In the present invention, the sputter coating may be any sputter coating known to those skilled in the art, and by way of example, magnetron sputtering, in the present invention, the specific operation steps of magnetron sputtering are as follows:
under the environment of argon and reaction gas, a bias power supply is turned on, a medium-frequency power supply of a target material required by coating is turned on, the non-metallic material is coated, the voltage of the bias power supply is set to be 80-180V, the duty ratio of the bias power supply is set to be 30-50%, the current of the medium-frequency power supply is set to be 15A-25A, the flow of argon is set to be 150 plus one of 180Sccm, the flow of the reaction gas is gradually added according to the requirement of a film system, the coating time is set according to the requirements of the film system and the film thickness, the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa；
After the film coating is finished, various pump valves are closed in sequence according to the operation specifications of the magnetron sputtering film coating machine, and the product is taken out after the gas is discharged and the door is opened.
In the invention, the metal layers formed by sputtering coating are a first metal layer and a second metal layer.
The first metal layer is a metal layer plated on the non-metal layer.
The thickness of each of the first metal layer and the second metal layer is 1-200 nm; more preferably 1-20 nm.
The metal material of the first metal layer and the second metal layer is at least one of the following metals or compounds thereof: ni, Co, Cu, and Ag.
Chemical plating
Electroless plating, also known as electroless plating or autocatalytic plating, is a plating method in which metal ions in a plating solution are reduced to metal by means of a suitable reducing agent in the absence of an applied current and deposited onto the surface of a part.
Electroless plating is a deposition process that produces metal by a controlled redox reaction under the catalytic action of the metal. Compared with electroplating, the chemical plating technology has the characteristics of uniform plating layer, small pin holes, no need of direct-current power supply equipment, capability of depositing on a non-conductor, certain special properties and the like.
In one embodiment of the present invention, the third metal layer formed by electroless plating is a copper film.
As an embodiment of the invention, the coating step of the electroless plating at least comprises one or more of copper plating and the following steps in combination;
the combination of steps comprises:
bulking, degumming, neutralizing, adjusting, activating and pretreating, activating and reducing.
Bulkiness
Bulking is a prerequisite to provide a uniform, desirable cell wall for subsequent steps.
The leavening agent used in the invention consists of water, leavening additive and pH correction agent; and each liter of leavening agent contains 849ml of water, 150ml of leavening additive and 1ml of pH correction agent.
The leavening additive consists of 30-100g/L of N-methyl pyrrolidone, 40-60g/L of sodium hydroxide and 30-100g/L of DMF.
The pH correction agent is a 32 wt% sodium hydroxide solution.
The bulking treatment steps are as follows:
placing the object to be treated in the leavening solution for 45-110s, wherein the temperature of the leavening solution is 70-80 ℃.
The leavening solution is a mixture of leavening agent and water, and 150ml of leavening additive is contained in 1 liter of leavening solution.
The pH value of the leavening solution is 10-12.
Degumming
The glue removal is mainly used for efficiently cleaning hole walls and drilling residues and effectively preventing the separation of the hole walls; meanwhile, the bonding force between the hole wall and the base material can be effectively increased, and the separation risk is reduced.
The degumming agent used in the invention consists of water, a degumming additive and a pH regulator; and each liter of leavening agent contains 770ml of water, 125ml of degumming additive and 105ml of pH regulator.
The degumming additive is permanganate, and sodium permanganate is preferred.
The pH regulator is 32% sodium hydroxide solution, and the 32% sodium hydroxide solution is 432g/L NaOH.
The glue removing treatment steps are as follows:
and placing the object to be treated in the degumming solution for 90-300s, wherein the temperature of the degumming solution is 75-85 ℃.
The degumming solution is a mixture of a degumming agent and water, and 1 liter of the degumming solution contains 50g of degumming additive; 1 liter of the degumming solution contained 45g of NaOH.
Neutralization
In the invention, the neutralization is to neutralize the acidic substances in the degumming process, so that the binding force is improved.
The neutralizer used in the invention consists of water, sulfuric acid, hydrogen peroxide and a neutralizing additive; and contains 860ml of water, 100ml of 50 wt.% sulfuric acid and 15ml of 35 wt.% H per liter of neutralizing agent 2 O 2 。
The neutralization treatment steps are as follows:
and placing the object to be treated in the neutralizing solution for 35-60s, wherein the temperature of the neutralizing solution is 25-35 ℃.
The neutralization solution is a mixture of a neutralizing agent and water, and 100ml of 50 wt% sulfuric acid is contained in 1 liter of the neutralization solution; 15ml of 35 wt% H 2 O 2 。
Adjustment of
The adjustment is to effectively remove residues of the degumming residue in the hole and adjust the charge of the hole wall, so that the hole wall becomes a surface with extremely strong adsorption capacity, and an ideal hole wall treatment effect is provided for subsequent copper plating.
The regulator used in the invention consists of water and a regulating additive; and each liter of conditioning agent contains 960ml of water, 40ml of conditioning additive.
The adjusting additive is selected from one of dopamine, dopamine hydrochloride, pyrrole, alcohol amine or nitrate.
The adjusting processing steps are as follows:
and (3) placing the object to be treated in the adjusting solution for 60s, wherein the temperature of the adjusting solution is 50 ℃.
Activation pretreatment
In the invention, the activation pretreatment is mainly used for treating pollutants in the holes before activation and adjusting electric charge to prepare for subsequent activation.
In the invention, the activation pretreatment agent is a sodium chloride solution, and each 1 liter of the activation pretreatment agent contains 980ml of water, 10ml of sodium chloride and 10ml of activation pretreatment additive.
The activating pretreatment additive is one of tartrate, citrate, ethylene diamine tetraacetic acid salt, nitrilotriacetate and triethanolamine.
The treatment steps of the activation pretreatment are as follows:
and (3) placing the object to be treated in the activation pretreatment agent for 20s, wherein the temperature of the neutralization solution is 25 ℃.
Activation of
The activation treatment in the invention is to activate the hole wall with adjusted charge so as to provide the best condition for good coverage of the subsequent copper plating.
The activating agent used in the invention consists of water, an activating additive and an alkaline substance; and each liter of activator contains 774ml of water, 225ml of activating additive and 1ml of sodium hydroxide solution.
The concentration of the sodium hydroxide solution was 32 wt%.
As an embodiment of the present invention:
the activating additive is a main component and an auxiliary agent; the weight ratio of the two is 10: 1.
the main component is palladium sulfate, and the auxiliary agent is ethylenediamine tetraacetic acid or ethylenediamine.
The process steps for the activation are now as follows:
placing the object to be treated in an activating solution for 45s, wherein the temperature of the activating solution is 45 ℃; the pH was 10.0.
As another embodiment of the present invention:
the activating additive is a main component and an auxiliary agent; the weight ratio of the two is 10: 1.
the main component is silver nitrate, and the auxiliary agent is sodium hypophosphite or EDTA disodium.
The process steps for the activation are now as follows:
placing the object to be treated in an activating solution for 45s, wherein the temperature of the activating solution is 45 ℃; the pH value is 3-6.
Activation reduction
The activation reduction is mainly used for catalyzing and accelerating the later copper plating process.
The activating and reducing agent used in the invention consists of water, boric acid and an activating and reducing additive; and 990ml of water, 25g of boric acid, 10mg of the reducing-activating additive per liter of reducing-activating agent.
The activating and reducing additive is potassium borohydride.
The treatment steps of the activation reduction are as follows:
placing the object to be treated in an activated reducing agent for 35s, wherein the temperature of the activated reducing solution is 35 ℃; the pH value is about 6.
Electroless copper plating
In the invention, every 1 liter of the chemical copper deposition solution contains 852.5ml of water, 85ml of copper base material, 2.5ml of copper stabilizer, 45ml of copper additive, 15ml of copper reducing agent and 9g of sodium hydroxide.
The copper base is a complexing agent selected from amino acids preferably having at least 2 or up to 10 carbon atoms, the acids of polycarboxylic acids, typically aminoacetic acids such as nitrilotriacetic acid, or, typically, alkylenepolyamine polyacetic acids including ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetetraacetic acid, 1, 3-diamino-2-propanol-N, N, N ', N ' -tetraacetic acid, dihydroxyphenylenediaminediaminediacetic acid, diaminocyclohexanetetraacetic acid or ethyleneglycol-bis [ (beta-aminoethyl ether) -N, N ' -tetraacetic acid ] and N, N, N ', N ' -tetrakis- (2-hydroxypropyl) ethylenediamine, citrate, tartrate, N, N-2- (hydroxyethyl) glycine, N-bis- (2-hydroxypropyl) ethylenediamine, citrate, tartrate, Gluconate, lactate, citrate, tartrate, crown ether and/or a mixture of acupuncture points.
The copper additive is copper sulfate.
The copper reducing agent is selected from vanillin and one or more of formaldehyde, glyoxylic acid, sodium hypophosphite or methyl citral.
The electroless copper plating method comprises the following processing steps:
the object to be treated is placed in the chemical copper deposition solution for 240-450s, and the temperature of the chemical copper deposition solution is 35 ℃.
The service life of the liquid medicine is as follows: production area of bath solution is 100m 2 The specific gravity of/L or bath solution exceeds 1.09g/cm 3 。
The thickness of the third metal is 0.05-3 μm.
Plating film
Electroplating is a process of plating a thin layer of other metals or alloys on the surface of some metals by using the principle of electrolysis, and is a process of adhering a layer of metal film on the surface of a metal or other material product by using the action of electrolysis, thereby playing the roles of preventing metal oxidation (such as corrosion), improving wear resistance, conductivity, light reflection, corrosion resistance (such as copper sulfate and the like), enhancing the appearance and the like.
The electroplating solution used in the invention contains 60-90g/L of blue vitriod; 180-220g/L sulfuric acid; 40-80ppm chloride ion; 8-12ml/L of a jar opening agent; 3-5ml/L of brightener and 0.1-0.5ml/L of regulator.
The source of the chloride ions in the invention is hydrochloric acid, acid mist or chloride ions in tap water.
The cylinder opener is sulfonate, nitrogen heterocyclic copolymer and surfactant.
The sulfonate is selected from one or more of sodium dodecyl sulfonate, sodium acyl methylamine alkane sulfonate or sodium p-toluenesulfonate; the nitrogen heterocyclic copolymer is poly (vinyl imidazole-2-acrylamide-2-methylpropanesulfonic acid-stearyl methacrylate). The surfactant is selected from one of sodium isethionate, dihexyl sodium sulfosuccinate and sodium dodecyl sulfate.
The brightener is sodium mercaptopropane sulfonate and sodium N, N-dimethyl-dithioformamide propane sulfonate, and the ratio of the brightener to the sodium N, N-dimethyl-dithioformamide propane sulfonate is 2: 1.
the regulator is polyethylene glycol with a hydroxyl value of 8-14 mg KOH/g.
The electroplating steps are as follows:
01. plating solution open cylinder
1. Cylinder cleaning
A) Cleaning the cylinder body and each pipeline by water;
B) soaking the cylinder body and the filtering system with 5 wt% of NaOH for 2-4 hours;
C) cleaning the cylinder body and each pipeline by clean water and then using 5 wt% of H 2 Soaking in SO4 for 2-4 hr;
D) cleaning the cylinder body and each pipeline by water and opening the cylinder;
2. step of opening cylinder
A) Adding 2/3-jar-volume water, starting filtration and inflation;
B) slowly adding 200g/L of AR-grade sulfuric acid;
C) adding 75g/L of copper sulfate;
D) hanging a cleaned copper anode, filtering for 4 hours by using a carbon core, and then replacing a cotton core for filtering;
E) when the temperature is cooled to below 30 ℃, 10ml/L of the jar-opening agent, 5ml/L of the brightening agent and 0.5ml/L of the regulator are added;
F) electrolyzing for 4-8 hours by using 0.5-2.0ASD current density;
G) and the trial and chemical analysis can be carried out after adjusting each component to the normal range.
02 electroplating conditions were as follows:
working temperature: 20-30 ℃; the cathode current density is 1-6A/dm 2 The voltage is 1-3.5V; the anode is a phosphor-copper ball or a phosphor-copper corner (containing 99.9 percent of copper)Phosphorus 0.03-0.06 wt%). The area ratio of the cathode to the anode is 1 (1.5-2.5); the stirring mode is air stirring (a low-pressure oil-free blower is adopted and passes through an oil-water separation device and a filtering device) and cathode movement; the filtration mode is continuous filtration with 5-10 μm cotton core or carbon core.
03 plating solution maintenance:
1. the plating solution lost due to evaporation can be supplemented by deionized water;
2. periodically analyzing the copper sulfate content, the sulfuric acid content and the chloride content;
3. adjusting the additive according to the hercules test;
4. 200ml of brightener is added for every 1000AH in normal production.
The thickness of the fourth metal layer is 100-50000 nm.
The technique of the present invention will be described in detail with reference to specific examples.
Example 1:
the present embodiment provides a non-metallic material surface metalized article comprising one non-metallic layer and four non-metallic layers;
the non-metal layer is a polyethylene film, and the weight average molecular weight of the polyethylene film is 560000.
The film thickness was 50 μm.
The four metal layers are respectively a first metal layer, a second metal layer, a third metal layer and a fourth metal layer.
The first metal layer and the second metal are plated in a sputtering mode, and the third metal layer is plated in a chemical plating mode; and plating the fourth metal layer in an electroplating mode.
The first metal layer is made of Ni metal, the second metal layer is made of Co metal, and the third metal layer and the fourth metal layer are both made of copper metal.
The sputtering mode is as follows:
s01, under the environment of argon and reaction gas, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, and coating the non-metal material, wherein the voltage of the bias power supply is set to be 95V, and the duty ratio of the bias power supply is increasedSetting the ratio at 35%, setting the current of the intermediate frequency power supply at 18A, setting the flow of argon at 160Sccm, gradually adding the reaction gas according to the requirement of the film system, setting the film coating time at 15min, and reducing the vacuum degree to 2.3 × 10 -1 Pa；
And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating, opening the door and taking out the product to obtain the product coated with the first metal layer.
And S02, according to the step S01, carrying out metallization operation of the second metal layer on the product plated with the first metal layer.
The metallization operation parameters of the second metal layer are as follows:
in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 150V, the duty ratio of the bias power supply is set to be 35%, the current of the medium-frequency power supply is set to be 22A, the flow of argon is set to be 150Sccm, the flow of the reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 9min, the vacuum degree is reduced to be 2.3 multiplied by 10, and the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa。
The thickness of the first metal layer is 15nm, and the thickness of the second metal layer is 13 nm;
chemical plating:
in the invention, the chemical plating comprises the following steps:
S001：
bulking: placing the sputtered and coated product in a swelling solution for 60s at 75 ℃;
S002：
removing glue: placing the bulked product in a degumming solution for 120s at 80 ℃;
S003
neutralizing: placing the product subjected to the degumming treatment in a neutralization solution for 40s, wherein the temperature of the neutralization solution is 30 ℃;
S004：
adjusting: and (3) placing the neutralized product in a regulator for 60s, and regulating the temperature of the solution to 50 ℃.
S005：
Activation pretreatment: the conditioned article was placed in an activated pre-treatment for 20 seconds at a neutralization solution temperature of 25 degrees celsius.
S006：
And (3) activation: the product after activation pretreatment is placed in an activating agent for 45s, and the temperature of the activating solution is 45 ℃.
S007：
Activation and reduction: and (3) placing the activated product in an activated reducing agent for 35s, wherein the temperature of the activated reducing agent is 35 ℃.
S008：
Copper plating: and (3) placing the product subjected to the activation reduction treatment in a chemical copper deposition solution for 315s, wherein the temperature of the chemical copper deposition solution is 35 ℃.
The swelling agent consists of water, a swelling additive and a pH correction agent; and each liter of leavening agent contains 849ml of water, 150ml of leavening additive and 1ml of pH correction agent. The pH correction agent is a 32 wt% sodium hydroxide solution.
The 150ml leavening additive consisted of 60g/L N-methyl pyrrolidone, 50g/L sodium hydroxide and 70g/L DMF.
The degumming agent consists of water, a degumming additive and a pH regulator; and each liter of degumming agent contains 770ml of water, 125ml of degumming additive and 105ml of pH regulator. The glue removing additive is sodium permanganate; the pH regulator is 32% sodium hydroxide solution, and the 32% sodium hydroxide solution is 432g/L NaOH.
The neutralizer consists of water, sulfuric acid, hydrogen peroxide and a neutralizing additive; and contains 885ml of water, 100ml of 50 wt.% sulfuric acid and 15ml of 35 wt.% H per liter of neutralizing agent 2 O 2 。
The regulator consists of water and a regulating additive; and each liter of the conditioner contains 960ml of water, 40mg of conditioning additive. The adjustment additive is dopamine.
The activating pretreatment agent is sodium chloride solution, and each 1 liter of the activating pretreatment agent contains 980ml of water, 10ml of sodium chloride and 10ml of triethanolamine.
The activating agent consists of water, an activating additive and an alkaline substance; and each liter of activator contains 774ml of water, 225ml of activating additive and 1ml of sodium hydroxide solution. The concentration of the sodium hydroxide solution was 32 wt%. The activating additive is a main component and an auxiliary agent; the weight ratio of the two is 10: 1.
the main component is palladium sulfate, and the auxiliary agent is ethylenediamine tetraacetic acid.
The activated reducing agent consists of water and boric acid; and 990ml of water, 25g of boric acid and 10mg of potassium borohydride per liter of activating-reducing agent.
The chemical copper deposition solution comprises 852.5ml of water, 85ml of copper base material, 2.5ml of copper stabilizer, 45ml of copper additive, 15ml of copper reducing agent and 9g of sodium hydroxide per 1 liter of chemical copper deposition solution. The copper base, copper stabilizer, copper additive and copper reducing agent were purchased from Guangdong Shuichi technologies, Inc.
The copper base agent is N-hydroxyethyl ethylene diamine tetraacetic acid; the copper additive is copper sulfate; the copper reducing agent is methyl citral.
Electroplating of
The electroplating steps are as follows:
01. plating solution jar
1. Cylinder cleaning
A) Cleaning the cylinder body and each pipeline by using water;
B) soaking the cylinder body and the filtering system for 3 hours by using 5 wt% of NaOH;
C) cleaning the cylinder body and each pipeline by clean water and then using 5 wt% of H 2 Soaking in SO4 for 2 hours;
D) cleaning the cylinder body and each pipeline by water and opening the cylinder;
2. step of opening cylinder
A) Adding water with the volume of 2/3 cylinders, and starting filtering and inflating;
B) slowly adding 200g/L of AR-grade sulfuric acid;
C) adding 75g/L of copper sulfate;
D) hanging a cleaned copper anode, filtering for 4 hours by using a carbon core, and then replacing the cotton core for filtering;
E) when the temperature is cooled to below 30 ℃, 10ml/L of jar opening agent, 5ml/L of brightening agent and 0.5ml/L of regulator are added;
F) electrolyzing for 6 hours by using 1.5ASD current density;
G) and the components can be adjusted to normal range by test and chemical analysis for trial production.
02 electroplating conditions were as follows:
working temperature: 25 ℃; the cathode current density is 4A/dm 2 The voltage is 1.8V; the anode is a phosphor-copper ball or a phosphor-copper corner (containing 0.03-0.06 wt% of phosphor) containing 99.9% of copper. The area ratio of the cathode to the anode is 1: 2; the stirring mode is air stirring (a low-pressure oil-free blower is adopted and passes through an oil-water separation device and a filtering device) and cathode movement; the filtration mode is continuous filtration with 5-10 μm cotton core.
03 plating solution maintenance:
1. the plating solution lost due to evaporation can be supplemented by deionized water;
2. periodically analyzing the copper sulfate content, the sulfuric acid content and the chloride content;
3. adjusting the additive according to the hercules test;
4. 200ml of brightener is added for every 1000AH in normal production.
The plating solution used in this example contained 80g/L of copper sulfate pentahydrate; 190g/L sulfuric acid; 60ppm chloride ion; 9ml/L of a jar opening agent; 4ml/L of brightening agent and 0.3ml/L of regulating agent. Hydrochloric acid is the source of chloride ions in this example.
The cylinder opener is sodium dodecyl sulfate, poly (vinyl imidazole-2-acrylamide-2-methylpropanesulfonic acid-stearyl methacrylate) and sodium hydroxyethyl sulfonate in a ratio of 5: 1: 1.
the brightener is sodium mercapto propane sulfonate and sodium N, N-dimethyl dithioformamide propane sulfonate, and the ratio is 2: 1.
the regulator is polyethylene glycol with hydroxyl value of 10mg KOH/g.
The thickness of the third metal layer is 1 μm; the thickness of the fourth metal layer is 300 nm.
Example 1-1:
the present example differs from example 1 as follows, with the remainder being the same:
the sputtering mode is as follows:
s01, under the environment of argon and reaction gas, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, performing film coating on a non-metal material, setting the voltage of the bias power supply to be 95V, setting the duty ratio of the bias power supply to be 35%, setting the current of the medium-frequency power supply to be 18A, setting the flow of argon to be 160Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the film coating time to be 18min, and reducing the vacuum degree to be 2.3 multiplied by 10 -1 Pa；
And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating and opening the door to take out the product, thereby obtaining the product coated with the first metal layer.
S02, according to the step S01, the product plated with the first metal layer is subjected to metallization operation of a second metal layer.
The metallization operation parameters of the second metal layer are as follows:
in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 150V, the duty ratio of the bias power supply is set to be 35%, the current of the medium-frequency power supply is set to be 22A, the flow of argon is set to be 150Sccm, the flow of the reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 6min, the vacuum degree is reduced to be 2.3 multiplied by 10, and the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa。
Example 2:
this embodiment differs from embodiment 1 in that the metal of the second metal layer is silver; and the specific operating parameters are as follows:
the sputtering mode is as follows:
s01, in an argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, coating the non-metal material, setting the voltage of the bias power supply to be 95V, the duty ratio of the bias power supply to be 35 percent, the current of the medium-frequency power supply to be 18A, setting the flow of argon to be 160Sccm, and gradually setting the flow of reaction gas according to the requirements of a film systemAdding, setting the film coating time for 15min, and reducing the vacuum degree to 2.3 × 10 -1 Pa；
And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating, opening the door and taking out the product to obtain the product coated with the first metal layer.
And S02, according to the step S01, carrying out metallization operation of the second metal layer on the product plated with the first metal layer.
The metallization operation parameters of the second metal layer are as follows:
in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 160V, the duty ratio of the bias power supply is set to be 40%, the current of the medium-frequency power supply is set to be 21A, the flow of argon is set to be 160Sccm, the flow of reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 10min, the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa。
The bulking treatment steps are as follows:
the object to be treated is placed in the leavening solution for 80s, and the temperature of the leavening solution is 78 ℃.
Example 3:
the present embodiment is different from embodiment 1 in that the metal of the first metal layer is Co metal, and the metal of the second metal layer is Ni metal.
The operating parameters were the same as in example 1, with the following operating parameters:
the sputtering mode is as follows:
s01, in an argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by coating, coating the non-metal material, setting the voltage of the bias power supply to 110V, the duty ratio of the bias power supply to 31%, the current of the medium-frequency power supply to 17A, setting the flow of argon to 166Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the coating time to 13min, and reducing the vacuum degree to 2.3 multiplied by 10 -1 Pa；
And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating, opening the door and taking out the product to obtain the product coated with the first metal layer.
And S02, according to the step S01, carrying out metallization operation of the second metal layer on the product plated with the first metal layer.
The metallization operation parameters of the second metal layer are as follows:
under the environment of argon and reaction gas, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 160V, the duty ratio of the bias power supply is set to be 40%, the current of the medium-frequency power supply is set to be 20A, the flow of argon is set to be 160Sccm, the flow of the reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 8min, the vacuum degree is reduced to be 2.3 multiplied by 10, and the target material is subjected to film coating -1 Pa。
The bulking treatment steps are as follows:
placing the object to be treated in the leavening solution for 70s, wherein the temperature of the leavening solution is 75 ℃.
The glue removing treatment steps are as follows:
and (3) placing the object to be treated in the degumming solution for 110s, wherein the temperature of the swelling solution is 81 ℃.
Example 3-1:
the present embodiment is different from embodiment 1 in that the metal of the first metal layer is Co metal, and the metal of the second metal layer is Ni metal; and the specific parameters are the same as in example 1.
Example 4:
this embodiment is different from embodiment 3 in that the metal of the second metal layer is Ag metal.
The operating parameters were the same as in example 3, with the following operating parameters:
the sputtering mode is as follows:
s01, in an argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by coating, coating the non-metal material, setting the voltage of the bias power supply to 110V, the duty ratio of the bias power supply to 31%, the current of the medium-frequency power supply to 17A, setting the flow of argon to 166Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the coating time to 13min, and reducing the vacuum degree to 2.3 multiplied by 10 -1 Pa；
And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating and opening the door to take out the product, thereby obtaining the product coated with the first metal layer.
And S02, according to the step S01, carrying out metallization operation of the second metal layer on the product plated with the first metal layer.
The metallization operation parameters of the second metal layer are as follows:
in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 120V, the duty ratio of the bias power supply is set to be 45 percent, the current of the medium-frequency power supply is set to be 20A, the flow of argon is set to be 155Sccm, the flow of reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 11min, the vacuum degree is reduced to be 2.3 multiplied by 10, and the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa。
The bulking treatment steps are as follows:
placing the object to be treated in the leavening solution for 90s, wherein the temperature of the leavening solution is 75 ℃.
The glue removing treatment steps are as follows:
the object to be treated is placed in the degumming solution for 112s, and the temperature of the leavening solution is 81 ℃.
Example 5:
this embodiment is different from embodiment 4 in that the metal of the first metal layer is Ag metal; the metal of the second metal layer is Co metal.
The operating parameters were the same as in example 4, with the following operating parameters:
the sputtering mode is as follows:
s01, in the argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by coating, coating the non-metal material, setting the voltage of the bias power supply to be 170V, the duty ratio of the bias power supply to be 32%, the current of the medium-frequency power supply to be 20A, setting the flow of argon to be 166Sccm, gradually adding the reaction gas according to the requirement of a film system, setting the coating time to be 15min, and reducing the vacuum degree to be 2.3 multiplied by 10 -1 Pa；
And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating, opening the door and taking out the product to obtain the product coated with the first metal layer.
And S02, according to the step S01, carrying out metallization operation of the second metal layer on the product plated with the first metal layer.
The metallization operation parameters of the second metal layer are as follows:
in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by coating is turned on, coating is started, the voltage of the bias power supply is set to be 120V, the duty ratio of the bias power supply is set to be 45%, the current of the medium-frequency power supply is set to be 21A, the flow of argon is set to be 158Sccm, the flow of the reaction gas is gradually added according to the requirement of a film system, the coating starting time is set to be 10min, the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa。
The bulking treatment steps are as follows:
placing the object to be treated in the leavening solution for 90s, wherein the temperature of the leavening solution is 75 ℃.
The glue removing treatment steps are as follows:
and placing the object to be treated in the degumming solution for 120s, wherein the temperature of the swelling solution is 80 ℃.
Example 6:
this embodiment is different from embodiment 5 in that the metal of the second metal layer is Ni.
The operating parameters were the same as in example 5, with the following operating parameters:
the sputtering mode is as follows:
s01, under the environment of argon and reaction gas, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, performing film coating on a non-metal material, setting the voltage of the bias power supply to be 170V, setting the duty ratio of the bias power supply to be 32%, setting the current of the medium-frequency power supply to be 20A, setting the flow of argon to be 166Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the film coating time to be 15min, and reducing the vacuum degree to be 2.3 multiplied by 10 -1 Pa；
And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating and opening the door to take out the product, thereby obtaining the product coated with the first metal layer.
And S02, according to the step S01, carrying out metallization operation of the second metal layer on the product plated with the first metal layer.
The metallization operation parameters of the second metal layer are as follows:
in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 125V, the duty ratio of the bias power supply is set to be 48%, the current of the medium-frequency power supply is set to be 20A, the flow of argon is set to be 150Sccm, the flow of the reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 10min, the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa。
The bulking treatment steps are as follows:
placing the object to be treated in the leavening solution for 90s, wherein the temperature of the leavening solution is 75 ℃.
Example 7:
this example differs from example 1 in that the sputter coating is only plated with one metal layer, i.e. a Ni metal layer.
Example 8:
the difference between this embodiment and embodiment 1 is that this embodiment provides a non-metallic material surface metalized product that does not contain a third metal layer, that is, it has no electroless plating layer, and only has two metal layers formed by sputtering and one metal layer formed by electroplating.
Example 9:
this example is different from example 1 in that the electroless plating does not include four steps of conditioning, pre-activation, activation and reduction-activation, and includes only the steps of bulking, degumming, neutralizing and copper plating.
Example 10:
this example is different from example 1 in that the non-metallic material is polypropylene, and the weight average molecular weight thereof is 30000.
The remaining operating parameters were in accordance with example 1.
Example 11:
this example differs from example 1 in that the copper reducing agent is formaldehyde.
Example 12:
this example differs from example 1 in that the degumming additive is potassium permanganate.
And (3) performance testing:
1. elongation of stretching
The test method comprises the following steps: a sample 10cm long by 10cm wide is taken and pulled horizontally with a constant force of 30N until it breaks, and the elongation is recorded.
The elongation (length at break-10)/10 × 100%.
2. Binding force
The test method comprises the following steps: taking a sample with the length of 10cm multiplied by the width of 10cm, adhering the sample by using a 3M adhesive tape, removing the adhesive tape, observing whether the metal on the surface of the sample is removed or not, and replacing the adhesive tape with different viscosity until the metal layer on the surface of the sample is damaged. And recording the adhesive specification of the adhesive tape, wherein the adhesive specification is related to the force, and converting to obtain the corresponding force.
3. Light transmittance
And observing the sample by using an optical microscope to observe whether the surface of the sample has light spots. The spot was found to be unacceptable, and the spot was found to be unacceptable.
And (3) testing results:
Figure BDA0002149578330000171
Figure BDA0002149578330000181
finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. A non-metallic material surface metalized article comprising one non-metallic layer and four metallic layers, wherein the non-metallic layer is a polyethylene film having a weight average molecular weight of 560000: the thickness of the film is 50 μm; the four metal layers are respectively a first metal layer, a second metal layer, a third metal layer and a fourth metal layer; the first metal layer and the second metal are plated in a sputtering mode, and the third metal layer is plated in a chemical plating mode; plating a fourth metal layer in an electroplating mode: the first metal layer is made of Ni metal, the second metal layer is made of Co metal, and the third metal layer and the fourth metal layer are both made of copper metal;
the sputtering mode is as follows:
s01 turning on bias power supply and medium frequency power supply of target material for coating under the atmosphere of xenon and reaction gas, coating the non-metal material, setting the voltage of bias power supply at 95V, the duty ratio of bias power supply at 35%, the current of medium frequency power supply at 18A, argon flow at 160Sccm, gradually adding the reaction gas according to the requirement of film system, setting the coating time at 15min, and reducing the straight air to 23 × 10 -1 Pa; after the coating is finished, closing various pump valves in sequence according to the operating specification of the Zhao magnetron sputtering coating machine, deflating and opening the door to take out the product, and obtaining the product plated with the first metal layer;
s02 according to the step S01, the product plated with the first metal layer is metallized by a second metal layer; the metallization operation parameters of the second metal layer are as follows: in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 150V, the duty ratio of the bias power supply is set to be 35%, the current of the medium-frequency power supply is set to be 22A, the flow of argon is set to be 150Sccm, the flow of the reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 9min, the vacuum degree is reduced to be 2.3 multiplied by 10, and the vacuum degree is reduced to be 2.3 multiplied by 10 -1 Pa; the thickness of the first metal layer is 15nm, and the thickness of the second metal layer is 13 nm;
the chemical plating comprises the following steps:
S001：
bulking: placing the sputtered and coated product in a swelling solution for 60s, wherein the temperature of the swelling solution is 75 ℃;
S002：
removing glue: placing the bulked product in a degumming solution, wherein the standing time is 120s, and the temperature of the degumming solution is 80 ℃;
S003：
neutralizing: placing the product subjected to the degumming treatment in a neutralizing solution for 40s, wherein the temperature of the neutralizing solution is 30 ℃;
S004：
adjusting: placing the neutralized product in a regulator for 60s, and regulating the temperature of the solution to 50 ℃;
S005：
activation pretreatment: placing the adjusted product in an activation pretreatment agent for 20s, wherein the temperature of a neutralization solution is 25 ℃;
S006：
and (3) activation: placing the product subjected to activation pretreatment in an activating agent for 45s, wherein the temperature of an activation solution is 45 ℃;
S007：
activation and reduction: placing the activated product in an activated reducing agent for 35s, wherein the temperature of the activated reducing agent is 35 ℃;
S008：
copper plating: placing the product subjected to activation reduction treatment in chemical copper precipitation liquid for 315s, wherein the temperature of the chemical copper precipitation liquid is 35 ℃;
the swelling agent consists of water, a swelling additive and a pH correction agent; and each liter of leavening agent contains 849ml of water, 150ml of leavening additive and 1ml of pH correction agent; the pH correction agent is 32 wt% sodium hydroxide solution; 150ml of leavening additive consists of 60g/L N-methyl pyrrolidone, 50g/L sodium hydroxide and 70g/L DMF;
the degumming agent consists of water, a degumming additive and a pH regulator; and each liter of the degumming agent contains 770ml of water, 125ml of degumming additive and 105ml of pH regulator; the adhesive removing additive is sodium permanganate; the pH regulator is 32% sodium hydroxide solution, and the 32% sodium hydroxide solution is 432 g/LNaOH;
the neutralizer consists of water, sulfuric acid, hydrogen peroxide and a neutralizing additive; and contains 885ml of water, 100ml of 50 wt.% sulfuric acid and 15ml of 35 wt.% H per liter of neutralizing agent 2 O 2 ；
The regulator consists of water and a regulating additive; and each liter of the regulator contains 960ml of water and 40mg of the regulating additive; the conditioning additive is dopamine;
the activating pretreatment agent is sodium chloride solution, and each 1 liter of the activating pretreatment agent contains 980ml of water, 10ml of sodium chloride and 10ml of triethanolamine;
the activating agent consists of water, an activating additive and an alkaline substance; and each liter of activator contains 774ml of water, 225ml of activating additive and 1ml of sodium hydroxide solution; the concentration of the sodium hydroxide solution is 32 wt%; the activating additive is a main component and an auxiliary agent, and the weight ratio of the main component to the auxiliary agent is 10: 1;
the main component is palladium sulfate, and the auxiliary agent is ethylene diamine tetraacetic acid;
the activating and reducing agent consists of water and boric acid: and each liter of the activating and reducing agent contains 990ml of water, 25g of boric acid and 10mg of potassium borohydride;
the chemical copper deposition solution per 1 liter comprises 852.5ml of water, 85ml of copper base agent, 2.5ml of copper stabilizer, 45ml of copper additive, 15ml of copper reducing agent and 9g of sodium hydroxide;
the copper base agent is N-hydroxyethyl ethylene diamine tetraacetic acid; the copper additive is copper sulfate; the copper reducing agent is methyl citral;
the electroplating steps are as follows:
01. plating solution jar
(1) Cleaning cylinder body
A) Cleaning the cylinder body and each pipeline by water;
B) soaking the cylinder body and the filtering system for 3 hours by using 5 wt% of NaOH;
C) cleaning the cylinder body and each pipeline by clean water and then using 5 wt% of H 2 SO 4 Soaking for 2 hours;
D) cleaning the cylinder body and each pipeline by water and opening the cylinder;
(2) and a step of opening the cylinder
A) Adding 2/3-jar-volume water, starting filtration and inflation;
B) slowly adding 200g/L of AR-grade sulfuric acid;
C) adding 75g/L copper sulfate;
D) hanging a cleaned copper anode, filtering for 4 hours by using a carbon core, and then replacing the cotton core for filtering;
E) when the temperature is cooled to below 30 ℃, 10ml/L of jar opening agent, 5ml/L of brightening agent and 0.5ml/L of regulator are added;
F) electrolyzing for 6 hours by using 1.5ASD current density;
G) testing and chemical analysis can be carried out after adjusting each component to a normal range;
02 electroplating conditions were as follows:
working temperature: 25 ℃; the cathode current density is 4A/dm2, and the voltage is 18V; the anode is a phosphor copper ball or a phosphor copper corner containing 999 percent of copper and contains 0.03 to 0.06 weight percent of phosphor; the area ratio of the cathode to the anode is 1: 2; the stirring mode is air stirring and cathode movement; the filtration mode is continuous filtration with 5-10 μm cotton core;
03 plating solution maintenance:
(1) the plating solution lost due to evaporation can be supplemented by deionized water;
(2) periodically analyzing the copper sulfate content, the sulfuric acid content and the chloride content;
(3) the additives were adjusted according to the hercules test:
(4) 200ml of brightener is added for every 1000AH operation in normal production
The electroplating solution comprises 80g/L of copper sulfate pentahydrate; 190g/L sulfuric acid; 60ppm chloride ion; 9ml/L of a jar opening agent; 4ml/L of brightener and 0.3ml/L of regulator: the source of the chloride ions is hydrochloric acid;
the cylinder opener is sodium dodecyl sulfate, poly (vinyl imidazole-2-acrylamide-2-methylpropanesulfonic acid-stearyl methacrylate) and sodium hydroxyethyl sulfonate, and the proportion is 5: 1: 1;
the brightener is sodium mercaptopropane sulfonate and sodium N.N-dimethyl-dithioformamide propane sulfonate, and the ratio of the brightener to the sodium N.N-dimethyl-dithioformamide propane sulfonate is 2: 1;
the regulator is polyethylene glycol with a hydroxyl value of 10 mgKOH/g;
the thickness of the third metal layer is 1 μm; the thickness of the fourth metal layer is 300 nm.
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