CN108456851B - Dry-type electroplating surface treatment method for zinc alloy - Google Patents

Dry-type electroplating surface treatment method for zinc alloy Download PDF

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CN108456851B
CN108456851B CN201810162682.4A CN201810162682A CN108456851B CN 108456851 B CN108456851 B CN 108456851B CN 201810162682 A CN201810162682 A CN 201810162682A CN 108456851 B CN108456851 B CN 108456851B
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zinc alloy
rgo
clps
graphene oxide
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CN108456851A (en
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赵铁军
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Mengcheng FanFeng Vacuum 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
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating

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Abstract

The invention provides a dry-type replacement electroplating surface treatment method of zinc alloy, which comprises the following steps: step S1, coating a base coat on the surface of the zinc alloy; step S2, sputtering an aluminum plating film on the workpiece obtained in the step S1 in a PVD furnace; step S3, plating a metal M color film on the workpiece in the step 2 in a PVD furnace; step S4, a finish is applied to the surface of the workpiece processed in step S3. By adopting the technical scheme of the invention, the electro-galvanized alloy imitation product with excellent functionality can be obtained, and the electro-galvanized alloy imitation product has outstanding corrosion resistance and excellent cold and heat cycle resistance; can replace the zinc alloy water electroplating process and is more environment-friendly.

Description

Dry-type electroplating surface treatment method for zinc alloy
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to a dry-type replacement electroplating surface treatment method for zinc alloy.
Background
Zinc alloy materials have many advantages such as low cost, excellent workability, excellent mechanical strength, etc., and thus have a wide range of technological applications. However, zinc alloys also have some drawbacks, such as too reactive surface properties, easy change in air, and easier reaction in water (acid, alkali, etc. environment). In addition, the die-casting condition of the zinc alloy is relatively harsh, holes are easy to be formed in the formed workpiece, the adverse factors cause the problems of poor corrosion resistance, short service life and the like of the zinc alloy, electroplating solution is often remained in the holes of the workpiece in the electroplating process of the zinc alloy to generate corrosion points, and once the corrosion points are formed, the corrosion points are easy to expand, so that the workpiece is embrittled, and the performance of the product cannot meet the requirements. And the generation of corrosion of the holes is avoided, and the electroplating start period of the zinc alloy needs to use highly toxic cyanide for hole sealing. This causes the electroplating pollution and the risk of the zinc alloy to be greatly increased. Although some scientific and technological units develop cyanide-free zinc alloy electroplating processes, the quality is unstable, and the cyanide-free zinc alloy electroplating processes cannot be widely popularized and used so far. Obviously, there is a need in the industry to develop an environmentally friendly surface treatment technique for zinc alloy with high functionality, excellent corrosion resistance and the same appearance as that of electroplated products.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a dry-type surface treatment method for replacing electroplating of zinc alloy, which solves the problems that the electroplating zinc alloy is not environment-friendly and has poor corrosion resistance.
In contrast, the technical scheme adopted by the invention is as follows:
a dry-type electroplating surface treatment method for zinc alloy comprises the following steps:
step S1, coating a base coat on the surface of the zinc alloy;
step S2, sputtering an aluminum plating film on the workpiece obtained in the step S1 in a PVD furnace;
step S3, plating a metal M color film on the workpiece in the step 2 in a PVD furnace;
step S4, a finish is applied to the surface of the workpiece processed in step S3.
By adopting the technical scheme, the principle that metal aluminum is more active than Zn is utilized, the surface of the zinc alloy is coated with the base coat, the base coat has better adhesive force, then the aluminizer is sputtered, when external oxygen and moisture permeate into the coating, Al firstly reacts, oxygen is consumed, the corrosion resistance is good, and the zinc alloy substrate is better protected. Wherein the metal M color film layer provides an apparent color. The top coat layer serves for better surface protection.
Preferably, in step S1, the base coat is an organic base coat; before the surface of the zinc alloy is coated with the bottom coat, the surface of the zinc alloy is coated with bottom water. Further, the thickness of the base coat is 6-20 μm. The organic base coat can be an organic base coat conventional in the art, such as a UV paint or a PU paint.
Preferably, in step S4, the finish paint is an organic finish paint; before the surface of the workpiece processed in step S3 is coated with the top coat, a primer layer is applied. Further, the thickness of the bottom water layer is 0.5-3 μm. Further, the thickness of the topcoat is 6-15 μm.
Preferably, the sum of the thicknesses of the sputtered aluminum-plated film and the metal M color film is 0.05-1 μ M.
In a further improvement of the present invention, in step S2, the thickness of the aluminum film is 0.01 to 1 μm; preferably, the thickness of the aluminum film is 0.01 to 0.5 μm.
As a further improvement of the present invention, step S2 further comprises co-plating an Al-M composite metal layer in a PVD furnace after sputtering the aluminum-plated film, wherein M is Cr, Al, Zn, Ti, Cu, Ni or their alloy combination.
By adopting the technical scheme, after the aluminum film is sputtered, the Al-M composite metal layer is co-plated in the PVD furnace, the Al-M composite metal layer is arranged between the sputtered aluminum film plating layer and the metal M color film layer, so that better interlayer bonding force is exerted, in addition, interlayer gradual transition is formed, at least two layers contain Al, better corrosion resistance is simultaneously exerted, and the corrosion speed is greatly reduced.
Preferably, the sum of the thicknesses of the Al-M composite metal layer and the metal M color film is 0.02-2 μ M; preferably, the sum of the thicknesses of the Al-M composite metal layer and the metal M color film is 0.05-0.5 μ M.
As a further improvement of the invention, before the step S1, a pretreatment bonding liquid is coated on the surface of the zinc alloy to form a pretreatment bonding layer.
As a further improvement of the invention, the pretreatment binding liquid is prepared by the following steps:
step A1, preparing a polymer RGO-ClPS of multilayer reduced graphene oxide micro-sheets grafted with chlorinated styrene;
and A2, preparing the nano aluminum particle-impregnated RGO-ClPS, mixing and stirring the nano aluminum particle-impregnated RGO-ClPS and resin to obtain the pretreatment binding liquid.
According to the technical scheme, the surface of the zinc alloy is pretreated firstly, so that the zinc alloy and the bottom coating have better binding power, in addition, the surface of the zinc alloy is subjected to pretreatment of a binding layer containing nano aluminum particles for impregnating RGO-ClPS, graphene has good conductivity, active electrons in a coating are conducted into aluminum, the zinc alloy is blocked from the outside, and the zinc alloy has better corrosion resistance.
As a further refinement of the present invention, step a1 includes the following sub-steps:
substep A101, preparing a graphene oxide grafted dichlorostyrene monomer GO-ClSM;
substep A102, reducing a graphene oxide grafted dichlorostyrene monomer GO-ClSM to obtain a multilayer reduced graphene oxide grafted dichlorostyrene monomer RGO-ClSM;
and a substep A103, carrying out polymerization reaction on the multilayer reduced graphene oxide grafted dichlorostyrene monomer RGO-ClSM to obtain the multilayer reduced graphene oxide micro-sheet grafted polymer RGO-ClPS.
Preferably, sub-step a101 comprises: adding graphene oxide micro-sheets and dichlorostyrene into a solvent, and stirring and mixing; then adding silver chloride, and carrying out reflux reaction for 12-24h at the temperature of 50-80 ℃; and after the reaction is finished, carrying out suction filtration, cleaning and vacuum drying to obtain a GO-ClSM monomer grafted by the multilayer Graphene Oxide micro-sheets, wherein SM represents a Styrene monomer, the meaning of a Styrene monomer, and GO represents Graphene Oxide.
Preferably, the molar ratio of the graphene oxide micro-sheets to dichlorostyrene is 1: 8-10.
Preferably, the solvent is a DMAC solution.
Preferably, the dosage of the silver chloride solution is 0.2-0.5% of the molar weight of the graphene oxide.
Preferably, the vacuum drying temperature is 70-90 deg.C, and the time is 30-60 min.
Preferably, the substep A102 comprises the steps of adding the prepared GO-ClSM into a hydrazine hydrate solution, refluxing for 18-24 hours at the oil bath temperature of 100-140 ℃, performing suction filtration, cleaning and vacuum drying after the reaction is finished, and obtaining the multilayer reduced graphene oxide microchip grafted monomer, namely RGO-ClSM. Further, the vacuum drying temperature is 70-90 deg.C, and the time is 20-30 min.
Preferably, substep A103 comprises mixing the prepared RGO-ClSM monomer with divinylbenzene and ethylene glycol dimethacrylate and then carrying out polymerization reaction to obtain the polymer RGO-ClPS grafted by the multi-layer reduced graphene oxide micro-sheets.
Further, substep A103 comprises adding the prepared RGO-ClSM monomer, divinylbenzene and ethylene glycol dimethacrylate into a pure water solution according to a molar ratio of 2:0.8-1.2:0.5-0.8, performing prepolymerization reaction for 10-30min at 40-60 ℃, then heating to 70-90 ℃ for reaction for 3-6h, washing the obtained product with water, and drying in a vacuum oven at 60-80 ℃ for 30-60min to obtain the polymer RGO-ClPS grafted by the multilayer reduced graphene oxide nanosheets.
As a further refinement of the present invention, step a2 includes the following sub-steps:
substep A201, impregnating and compounding a polymer RGO-ClPS grafted by multilayer reduced graphene oxide micro-sheets and nano aluminum paste to obtain an RGO-ClPS impregnated by nano aluminum particles;
and a substep A202 of mixing the RGO-ClPS impregnated with the nano aluminum particles with a resin, an auxiliary agent and a solvent to obtain a pretreatment binding liquid.
Preferably, the substep A201 comprises the step of uniformly mixing RGO-ClPS, nano aluminum paste, dimethyl amide and sodium dodecyl benzene sulfonate at the temperature of 60-80 ℃ to obtain the RGO-ClPS impregnated with the nano aluminum particles, wherein RGO/Al-ClPS is used as a code for short.
Preferably, the weight ratio of RGO-ClPS, nano aluminum paste, dimethyl amide and sodium dodecyl benzene sulfonate is 1: 0.3-0.8: 2-4: 0.05-0.2.
Preferably, the weight ratio of RGO-ClPS, nano aluminum paste, dimethyl amide and sodium dodecyl benzene sulfonate is 1: 0.5: 3:0.1.
Preferably, the particle size of the aluminum particles in the nano aluminum paste is 5-100 nm; preferably, the particle size of the aluminum particles in the nano aluminum paste is 5-20 nm.
As a further improvement of the invention, the pretreatment binding liquid comprises the following components in percentage by weight: 5-10% of nano aluminum particles impregnated RGO-ClPS, 10-20% of resin, 0.5-3% of adhesion promoter, 0.3-2% of dispersant, 0.2-0.5% of flatting agent and the balance of solvent.
As a further improvement of the invention, the resin is one or more of polyamide, polyacrylate, epoxy resin, phenolic resin, polyurethane and neoprene.
As a further improvement of the invention, the adhesion promoter is one or more combinations of silane coupling agent, chlorinated PP or phosphate ester functional monomer.
As a further improvement of the invention, the dispersing agent is calcium stearate, zinc stearate or magnesium stearate.
As a further improvement of the present invention, the leveling agent is an acrylic leveling agent.
As a further improvement of the invention, the thickness of the pre-treatment bonding layer is 2-5 μm.
Preferably, the thickness of the topcoat is from 6 to 15 μm.
The invention provides a zinc alloy high-functional surface treatment process with an imitation electroplating appearance, which discloses a pretreatment layer with excellent barrier and bonding properties, wherein a multi-layer reduced graphene oxide microchip graft polymer is impregnated and compounded by nano aluminum paste, then the composite material is sprayed on a zinc alloy blank together with resin, solvent and the like to form adhesive liquid, and the adhesive liquid is dried to form the pretreatment layer. And then spraying an organic base coat on the surface of the zinc alloy, drying, transferring the zinc alloy into PVD equipment to carry out composite metal coating, and finally spraying a layer of organic top coat to obtain the electro-galvanized alloy product with excellent functionality, wherein the anti-corrosion property is very outstanding.
Further, the process steps of the invention are as follows:
(1) preparing a polymer RGO-ClPS of multilayer reduced graphene oxide micro-sheet grafted chlorinated styrene.
(2) Preparing nanometer aluminum paste impregnation RGO-ClPS and preparing pretreatment binding liquid:
mixing the prepared RGO-ClPS with a nano aluminum paste auxiliary agent, dimethyl amide, sodium dodecyl benzene sulfonate and the like, heating and stirring uniformly at the temperature of 60-80 ℃ for 10-30min to obtain a nano aluminum impregnated composite RGO-ClPS solution, compounding the solution with resin, a solvent, a leveling agent and the like to directly spray the solution on a zinc alloy rubber part, and drying to form a pretreatment layer for sealing water vapor and promoting adhesion.
(3) And (3) spraying a coating on the zinc alloy workpiece obtained in the step (2), wherein a high-gloss organic base coat can be formed after drying PU or UV paint.
(4) Transferring the workpiece treated in the step (3) into a PVD furnace to carry out vacuum continuous composite coating of Al/Al-M/M.
(5) Taking the workpiece coated with the alloy film out of the PVD furnace, spraying a layer of bottom water (metal adhesion promoter) with the thickness of about 1-2 μm, spraying a layer of PU or UV coating (with the thickness of about 6-20 μm), and drying to form a protective organic top coat.
The above process constitutes one kind of dry environment friendly surface treating technology for zinc alloy and may be used to replace water electroplating process for zinc alloy.
Preferably, M may be Cr, Al, Zn, Ti, Cu, Ni, Zr, or a combination alloy thereof.
Compared with the prior art, the invention has the beneficial effects that:
by adopting the technical scheme of the invention, the electro-galvanized alloy imitation product with excellent functionality can be obtained, and the electro-galvanized alloy imitation product has outstanding corrosion resistance and excellent cold and heat cycle resistance. The invention provides a dry-type environment-friendly surface treatment technology for zinc alloy, which can replace a zinc alloy water electroplating process and is more environment-friendly.
Drawings
FIG. 1 is a flow chart of the surface treatment process of dry type spray-galvanized alloy with a modified RGO-ClPS-Al bonding layer according to example 1 of the present invention.
FIG. 2 is a flow chart of the surface treatment process of the dry type spray-galvanized alloy without the modified RGO-ClPS-Al bonding layer in example 2 of the present invention.
FIG. 3 is a sectional view showing a zinc alloy plated surface-treated product according to example 1 of the present invention.
FIG. 4 is a flowchart showing a conventional process for cyanide electroplating a zinc alloy blank according to comparative example 1.
FIG. 5 is a flow chart of the process of the improved cyanide-free electrogalvanized zinc alloy blank of comparative example 2.
FIG. 6 is a flowchart of a general dry spray zinc alloy surface treatment process of comparative example 3.
FIG. 7 is a flow chart of the improved dry type spray zinc alloy surface treatment process of example 3 of the present invention.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Preferably, the method for treating the surface of the zinc alloy by dry-type plating comprises the following steps:
step 1, preparing a polymer RGO-ClPS of multilayer reduced graphene oxide micro-sheets grafted with chlorinated styrene;
step 1-1, firstly preparing a graphene oxide grafted dichlorostyrene monomer GO-ClSM;
adding Graphene Oxide micro-sheets and dichlorostyrene into a DMAC solution according to a molar ratio of 1: 8-10, stirring and mixing for 10-30min, then adding a silver chloride solution accounting for 0.2-0.5% of the molar weight of the Graphene Oxide, carrying out reflux reaction for 12-24h at the temperature of 50-80 ℃, carrying out suction filtration after the reaction is finished, cleaning with analytically pure ethyl acetate, and then drying in a vacuum oven at the temperature of 80 ℃ for 30-60min to obtain a multilayer Graphene Oxide micro-sheet grafted GO-ClSM monomer, wherein SM represents Styrene monomer, meaning of Styrene monomer, and GO represents Graphene Oxide.
Step 1-2, reducing GO-ClSM into RGO-ClSM (multilayer reduced graphene oxide grafted dichlorostyrene monomer);
adding the GO-ClSM prepared in the step 1-1 into a hydrazine hydrate solution, refluxing for 18-24 h at 120 ℃ in an oil bath, performing suction filtration after the reaction is finished, cleaning with analytically pure water, and drying in a vacuum oven at 80 ℃ for 20-30min to obtain the multilayer reduced graphene oxide microchip grafted monomer, namely RGO-ClSM.
Step 1-3, preparing polymer RGO-ClPS;
adding the RGO-ClSM monomer prepared in the step 1-2, divinylbenzene and ethylene glycol dimethacrylate into a pure water solution according to a molar ratio of 2:1:0.5-0.8, performing prepolymerization reaction at 50 ℃ for 10-30min, heating to 80 ℃ for reaction for 3-6h, washing the obtained product with water, and drying in a vacuum oven at 60-80 ℃ for 30-60min to obtain the polymer RGO-ClPS grafted by the multilayer reduced graphene oxide micro-sheets.
Step 2, preparing nano aluminum paste to infiltrate RGO-ClPS and preparing a pretreatment binding liquid;
step 2-1, impregnating RGO-ClPS with nano aluminum paste for compounding: taking RGO-ClPS and nano aluminum paste (the particle diameter of aluminum particles is 5-100nm), dimethyl formamide and sodium dodecyl benzene sulfonate according to the weight ratio of 1: 0.5: 3:0.1, and the RGO-ClPS is obtained by evenly dispersing under the condition of 60-80 ℃ and 10-30min, and the RGO/Al-ClPS is used as a code number for short.
Step 2-2, preparing a pretreatment bonding layer solution;
and (2) putting the nano aluminum particle impregnated RGO-ClPS solution obtained in the step (2-1) into resin and solvent, and stirring for 30-60min to obtain a pretreatment binding solution, wherein the pretreatment binding solution comprises the following components in percentage by weight:
(1) the infiltration of the nano aluminum particles with RGO-ClPS accounts for 5 to 10 percent;
(2) the resin (one or more of polyamide, polyacrylate, epoxy resin, phenolic resin, polyurethane and chloroprene rubber) accounts for 10-20%
(3) The adhesion promoter (one or more of silane coupling agent, chlorinated PP or phosphate functional monomer) is 0.5-3%
(4) The dispersant (calcium stearate or magnesium stearate) is 0.5-2%
(5) The content of the flatting agent (acrylic acid) is 0.2-0.5%
(6) The balance of the solvent accounts for 64.5 to 83.8 percent
The pre-treatment binding liquid can be sprayed on a zinc alloy blank and dried (50-60 ℃ for 2-5min) to form a pre-treatment layer which can block water vapor and promote the adhesion of organic coating (especially UV type coating). The pre-treated bonding layer is given the reference RGO-ClPS-Al.
Step 3, spraying an organic base coat;
and (4) spraying a layer of PU or UV paint on the zinc alloy workpiece obtained in the step S2, and drying to form a high-gloss mirror-surface organic base coat, wherein the thickness of the coating is 6-15 mu m.
And 4, transferring the zinc alloy workpiece sprayed with the organic base coat into a PVD furnace to implement a special Al/Al-M/M vacuum continuous composite coating.
Step 4-1, vacuumizing the PVD furnace to 7 x 10-3Pa, introducing 100-300SCCM of oxygen flow, and performing plasma glow cleaning on the surface of the workpiece by using 300-500V of plasma source voltage3-5 min. And then starting the sputtering aluminizer. The power current of the aluminum target is 8-15A, the bias voltage is 380-400V, and the argon flow is 100-150 SCCM. The aluminum plating time is 3min per plating and 3-5min (cooling), which is a cycle. The aluminum is sputtered for 4-6 times in total, and 4 cycles of sputtering are carried out for 12 min. If the total coating time is less than 12min or the thickness of the sputtered aluminum film is less than 0.1 mu, the corrosion resistance of the product is poor, namely the product cannot pass the corrosion resistance CASS 8h test easily.
And 4-2, starting the Al-M composite coating after the sputtering of the aluminum coating film is finished. When M represents one of metals such as aluminum, nickel, titanium, copper, zirconium and the like or an alloy of any two of the metals, and chromium represents M, the operation method of the composite coating film comprises the following steps:
(1) starting the current chromium plating and the sputtering aluminum plating at the same time;
(2) the current of the electric arc chromium target is 60-80A, and the current of the sputtering aluminum target is 8-15A;
(3) the flow of the introduced argon is 100-00 SCCM;
(4) the plating time is 4min after each plating, namely, the current is cooled to zero for 5 min.
This is a co-plating period, and the total plating period is 2-3.
Step S403, after the co-plating, arc plating of the non-ferrous metal film is immediately performed as an appearance color. Take the bright chrome color as an example: starting the arc chromium target, adjusting the power supply to 60-90A, and introducing 100-200SCCM argon flow. The film coating process is that the cooling is stopped for 5min when the film is coated for 3min, which is a period, and the total co-coating of the nonferrous metal film requires 3-4 periods. The bottom layer is 5-20 μm.
And 5: spraying organic finish paint;
spraying the workpiece obtained in the step 4 with a layer of organic coating with the thickness of about 5-20 μm to protect the surface, wherein the coating comprises one of PU paint, lacquer or UV paint.
Example 1
After 40 zinc alloy die-cast blanks are cleaned and dried, according to the process flow of the technical scheme of the invention, as shown in fig. 1, the dry method is used for replacing the electroplating surface treatment, and the metal with the metal color and appearance used in the embodiment is chromium, namely M is Cr. The method comprises the following steps:
step 1, preparing a polymer RGO-ClPS of multilayer reduced graphene oxide micro-sheet grafted chlorinated styrene according to the steps 1-1, 1-2 and 1-3. Wherein the reaction molar ratio of the RGO-ClSM monomer to the divinylbenzene and the ethylene glycol dimethacrylate is 2:1: 0.6;
step 2, preparing a pretreatment binding liquid for impregnating the nano aluminum according to the steps 2-1 and 2-2, and spraying the pretreatment binding liquid on a zinc alloy blank, wherein the components and the weight percentage of the formula are as follows:
1) the nano aluminum particles are impregnated with RGO-ClPS 5%;
2) 10 percent of polyurethane resin
3) 5 percent of epoxy resin
4) 2 percent of alkyl acrylate phosphate ester monomer
5) 1 percent of silane coupling agent
6) 0.3 percent of dispersant zinc stearate
7) 0.2 percent of acrylic leveling agent
8) The balance of n-butanol and xylene as solvents is 76.5 percent
And 3, spraying a layer of UV (ultraviolet) base coat on the zinc alloy workpiece according to the step 3, wherein the thickness is about 15 mu m.
And 4, transferring the workpiece into a PVD furnace according to the step 4, and plating an Al/Al-Cr/Cr film according to the procedures of the steps 4-1,4-2 and 4-3, wherein the thickness of the sputtered aluminum is about 0.2 μm, the thickness of the co-plated Al-Cr alloy film is about 0.05 μm, and the thickness of the arc-plated Cr film is about 0.05 μm.
And 5, spraying a layer of commercially available bottom water (metal adhesion promoting liquid) on the workpiece obtained in the step 4, wherein the film thickness is about 1.5 microns, and then spraying a layer of UV finish paint with the thickness of about 12 microns.
The cross-sectional structure of the zinc alloy plated surface-treated product obtained in this example is shown in fig. 3.
Example 2
After 40 zinc alloy die-cast blanks are cleaned and dried, according to the process flow of the technical scheme of the invention, as shown in fig. 1, a dry method is implemented to replace electroplating surface treatment, wherein the metal with the metal color appearance used in the embodiment is zirconium, that is, M is Zr. The method comprises the following steps:
step 1, preparing a polymer RGO-ClPS of multilayer reduced graphene oxide micro-sheet grafted chlorinated styrene according to the steps 1-1, 1-2 and 1-3. Wherein the reaction molar ratio of the RGO-ClSM monomer to the divinylbenzene and the ethylene glycol dimethacrylate is 2:1: 0.6;
step 2, preparing a pretreatment binding liquid for impregnating the nano aluminum according to the steps 2-1 and 2-2, and spraying the pretreatment binding liquid on a zinc alloy blank, wherein the components and the weight percentage of the formula are as follows:
1) the nano aluminum particles are impregnated with RGO-ClPS 5%;
2) 8 percent of polyurethane resin
3) 7 percent of epoxy resin
4) 2 percent of alkyl acrylate phosphate ester monomer
5) 1 percent of silane coupling agent
6) 0.5 percent of dispersant
7) 0.3 percent of flatting agent
8) The balance of n-butanol and xylene as solvents is 76.2 percent
And 3, spraying a UV (ultraviolet) base coat on the zinc alloy workpiece (coated with the pretreatment bonding layer) according to the step 3, wherein the thickness is about 12 microns.
Step 4, transferring the workpiece into a PVD furnace according to the step 4, and plating an Al/Al-Zr/Zr continuous film according to the procedures of the steps 4-1,4-2 and 4-3, wherein the thickness of the sputtered aluminum film is about 0.25 μm, and the thickness of the co-plated Al-Zr alloy film is about 0.05 μm; when the Zr film is plated by electric arc, nitrogen with the flow rate of 150SCCM and argon with the flow rate of 100SCCM are introduced, the Zr target current is 120A, the plating time is totally 12min, and the film thickness is about 0.03 mu m.
And 5, spraying a layer of commercially available bottom water (metal adhesion promoting liquid) on the workpiece obtained in the step 4, wherein the film thickness is about 2 microns, and then spraying a layer of UV finish paint with the thickness of about 14 microns.
The zinc alloy handle obtained by the method has light golden appearance.
Example 3
Taking 40 zinc alloy die-casting blanks, cleaning and drying the zinc alloy die-casting blanks, and then implementing dry method instead of electroplating surface treatment according to the process flow of the technical scheme of the invention as shown in figure 2, wherein in the embodiment, the pretreatment of the binding liquid is not adopted, and the commercially available bottom water is used instead, so that the step 1 does not exist; in addition, the metal with metallic appearance used in this example is chromium, i.e., M is Cr. The method comprises the following steps:
step 1, since RGO-ClPS was not employed, this step was not present as compared with example 1.
And 2, spraying a layer of commonly-used bottom water (metal adhesion promoting liquid) purchased from the market on the zinc alloy blank, wherein the thickness of the film is about 2 microns.
And 3, spraying a layer of UV paint on the zinc alloy workpiece obtained in the step 2, wherein the thickness of the paint film is about 15 mu m.
And 4, feeding the zinc alloy workpiece which is sprayed with the UV primer in the step 3 into a PVD furnace, and plating an Al/Al-Cr/Cr continuous film according to the procedures of the above examples 4-1,4-2 and 4-3, wherein the thickness of the sputtered aluminum layer is about 0.25 μm, the thickness of the co-plated Al-Cr alloy film is about 0.05 μm, and the thickness of the appearance arc plating Cr film is about 0.05 μm.
And 5, removing the zinc alloy workpiece obtained in the step 4 out of the PVD equipment. A layer of commercially available primer was applied in a thickness of about 2 μm, followed by a layer of UV topcoat in a thickness of about 14 μm.
Although the zinc alloy dry-method-substituted electroplating surface treatment product obtained in the embodiment is inferior to the zinc alloy dry-method-substituted electroplating surface treatment products obtained in the embodiment 1 and the zinc alloy dry-method-substituted electroplating surface treatment product obtained in the embodiment 2 in functionality, the binding force (5B) and the cold and heat cycle passing rate are up to 90%, and the corrosion-resistant side passing rate of CASS 4h is 80%, so that the zinc alloy dry-method-substituted electroplating surface treatment product can still be.
Comparative example 1
Taking 40 zinc alloy die-casting blanks, cleaning, drying, and performing electrodeposition according to the conventional industrial cyanide electrogalvanizing process, wherein the process flow chart is shown in FIG. 4. The method comprises the following steps:
i, performing ultrasonic washing to remove oil and wax from 40 zinc alloy die-casting blanks, and then performing cathodic electrolysis to remove oil, wherein the anode is a stainless steel plate or a stainless steel net (304 or 316 material), the cathode is the zinc alloy blanks, and the current density is controlled to be 3A/dm2The electrolysis time was about 15 s. After completion, 30s of anodic electrolytic degreasing (current density about 0.5A/dm) is carried out under the condition of high standard requirement2) The binding force is improved.
And step ii, activating by using 40% by mass of HF, wherein the concentration of HF is 12-15ml/L, the concentration of boric acid is 3-5g/L, and the activation time at room temperature is about 30 s.
Step iii, then using 10g/L zinc cyanide and 25g/L cuprous cyanide as the base copper for cyanide pre-plating with a current density of about 1A/dm2And controlling the pH value of the bath solution to be about 10, and pre-plating for about 80s at room temperature.
And iv, activating by using dilute sulfuric acid, wherein the activation time is about 3 min.
Step v, carrying out conventional circuit copper sulfate;
and step vi, carrying out conventional nickel electroplating (containing seminickel and all-nickel), wherein the thickness of the nickel layer is about 15 mu m.
Step vii, chromic acid activation (chromic acid content of about 3 g/L) is carried out, then hexavalent chromium or trivalent chromium is electroplated, and the thickness of the chromium film is about 0.2 μm.
The zinc alloy obtained by the process has bright chromium color on the surface. If other colors are to be obtained, such as golden yellow, bronze, stainless steel, etc., the zinc alloy workpiece after chrome plating must be transferred to a PVD furnace for vacuum plating.
The process adopts the cyanide with high toxicity, and uses the hexavalent chromium with high pollution hazard in the process, so the process is not environment-friendly.
Comparative example 2
Taking 40 zinc alloy die-casting blanks, cleaning and drying the blanks, and then carrying out electrodeposition operation according to the improved cyanide-free electrogalvanizing process shown in figure 5. The method comprises the following steps:
step i, 40 zinc alloy die-casting blanks are washed by ultrasonic water to remove oil and wax, and then cathode electrolysis is carried out to remove oil. The voltage is 3V, the anode is a stainless steel plate, the cathode is a zinc alloy blank, and the current density is controlled to be 3A/dm2。
And step ii, activating in a dilute hydrochloric acid tank, wherein the liquid temperature is room temperature, 6g/L HCl is used, and the activation time is about 45 s.
And iii, performing two-stage cyanide-free pre-plating of bottom copper, wherein the bath temperature is controlled to be about 55 ℃, and the pH value of bath solution is controlled to be 8.3-9.6. The bath solution comprises 40g/L of copper sulfate, about 280ml/L of accelerator and stabilizer respectively, and the total electroplating time is 10 min.
And iv, activating by using 1-2% of sulfuric acid by mass percentage for 3 min.
Step v, carrying out conventional circuit copper sulfate;
and step vi, carrying out conventional nickel electroplating (containing seminickel and all-nickel), wherein the thickness of the nickel layer is about 15 mu m.
Step vii, chromic acid activation (chromic acid content of about 3 g/L) is carried out, then hexavalent chromium or trivalent chromium is electroplated, and the thickness of the chromium film is about 0.2 μm.
The process does not use toxic cyanide, but still uses highly polluting hexavalent chromium plating operations. The more adverse factors are unstable quality and poor product corrosion resistance, the CASS 4h side-view pass rate is about 50%, even if the thickness of each electroplated layer is increased (+ 10-30%), the improvement effect is still not obvious, and the method is not easy to popularize industrially.
Comparative example 3
Taking 40 zinc alloy die-casting blanks, cleaning, drying, and carrying out a surface treatment process of dry spraying according to the process shown in figure 6. The method comprises the following steps:
step 1, spraying a layer of commercially available bottom water (metal adhesion promoter) on the zinc alloy die-casting blank, wherein the thickness of the bottom water is about 1-2 mu m.
And 2, spraying a layer of UV primer on the zinc alloy workpiece prepared in the step 1, wherein the thickness of the paint film is about 15 mu m.
Step 3, the zinc alloy workpiece sprayed with the UV primer is sent into a PVD furnace for single metal coating, and the adopted metal target can be one of chromium, aluminum, nickel, zirconium, titanium, copper and the like, or an alloy of any two of the chromium, aluminum, nickel, zirconium, titanium, copper and the like; the plating method used may be arc plating or sputtering plating. The target material used in this example was aluminum, and the coating method used was arc coating.
And 4, taking the zinc alloy workpiece prepared in the step 3 out of the PVD furnace, spraying a layer of bottom water with the thickness of about 2 microns, and then spraying a layer of UV finish paint with the thickness of about 15 microns.
Although the process of the zinc alloy dry surface treatment product prepared by the comparative example is environment-friendly, the corrosion resistance is poor, the test pass rate of CASS 4h is only 30%, and the commercial mass production condition is not met.
In this example, if the target metal is changed to copper, titanium, aluminum or nickel, the corrosion-resistant CASS 4h pass rate is not more than 50%.
Example 4
Taking 40 zinc alloy die-casting blanks, cleaning, drying, and carrying out a surface treatment process of dry spraying according to the process shown in figure 7. The method comprises the following steps:
step 1, spraying a layer of commercially available bottom water (metal adhesion promoter) on the zinc alloy die-casting blank, wherein the thickness of the bottom water is about 1-2 mu m.
And 2, spraying a layer of UV primer on the zinc alloy workpiece prepared in the step 1, wherein the thickness of the paint film is about 14-15 microns.
And 3, sending the zinc alloy workpiece sprayed with the UV primer into a PVD furnace, and carrying out the following steps:
(1) an aluminum target was used, the surface of the workpiece was coated with an aluminum film by sputtering, the power current of the target was 12A, the argon flow rate was 100SCCM, and the thickness of the sputtered aluminum film was about 0.25. mu.m.
(2) Then plating a chromium film by using an arc target; the current of the target is 70A, the flow of the introduced argon is 100SCCM, and the total chromium plating time is 12 min.
And 4, taking the zinc alloy workpiece prepared in the step 3 out of the PVD furnace, spraying a layer of bottom water with the thickness of about 2 microns, and then spraying a layer of UV finish with the thickness of about 15 microns.
The zinc alloy dry surface treatment product prepared by the embodiment has an environment-friendly process, the corrosion resistance is equivalent to that of the cyanide-free electroplating process in the comparison example 2, namely, the cyanide-free electroplating process in the figure 5, but the cold and heat cycle resistance is much better than that in the figure 5, so that the zinc alloy dry surface treatment product can be accepted by the market with relaxed quality requirements.
The properties of examples 1 to 4 and comparative examples 1 to 3 were measured and compared as shown in Table 1.
Table 1 table comparing functionality of examples 1 and 2 with comparative examples 1,2 and 3
Wherein, the passage of the falling sand (16 liters) impact test and the passage of the cold-hot cycle test (the condition is: -30 +/-3 ℃/h → 20 +/-5 ℃/h → 65 +/-3 ℃/h cold-hot impact for 20 times) is that no bubble separation layer appears on the surface, the surface does not bubble, and the surface bubbles represent the non-passage. The CASS corrosion resistance test passed the test that the surface did not peel off, blister or develop corrosion points.
From the functional test results of table 1, it can be concluded:
1) examples 1 and 2 are versions of the process of the present invention, which are excellent in both cold and heat cycle resistance, and particularly excellent in corrosion resistance, i.e., the test pass rate of CASS 4H, 8H can reach 100%, and can be used to replace the water electroplating process.
2) Example 3 is also a solution according to the invention, which is sub-optimal with respect to both the resistance to cold and heat cycles and the corrosion resistance. When the requirement of corrosion resistance is not particularly strict, it can be used for commercial production and can also be used to replace water electroplating.
3) The comparative examples 1 and 2 belong to the plating process, which is inferior in corrosion resistance and poor in cold and hot shock resistance, and the corrosion resistance can be improved unless the die casting or extrusion process is improved and the thickness of the plating layer is increased.
4) The corrosion resistance of comparative examples 3 and 2 was not stable and good enough to replace the water plating process.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (9)

1. A dry-type electroplating surface treatment method of zinc alloy is characterized in that: which comprises the following steps:
step S1, coating a base coat on the surface of the zinc alloy;
step S2, sputtering an aluminum plating film on the workpiece obtained in the step S1 in a PVD furnace;
step S3, plating a metal M color film on the workpiece in the step 2 in a PVD furnace;
step S4, coating finish paint on the surface of the workpiece processed in the step S3;
before the step S1, the method further comprises the steps of coating pretreatment binding liquid on the surface of the zinc alloy to form a pretreatment binding layer; the pretreatment binding liquid is prepared by the following steps:
step A1, preparing a polymer RGO-ClPS of multilayer reduced graphene oxide micro-sheets grafted with chlorinated styrene;
and A2, preparing the nano aluminum particle-impregnated RGO-ClPS, mixing and stirring the nano aluminum particle-impregnated RGO-ClPS and resin to obtain the pretreatment binding liquid.
2. The method of claim 1, wherein the aluminum film has a thickness of 0.01 ~ 1 μm in step S2.
3. The method for dry-type alternate plating surface treatment of zinc alloy according to claim 1, characterized in that: step S2 further includes co-plating an Al-M composite metal layer in a PVD furnace after sputtering the aluminum plating film, wherein M is Cr, Zn, Ti, Cu, Ni, Zr, or an alloy of any two combinations thereof.
4. The method for dry-type alternate plating surface treatment of zinc alloy according to claim 1, characterized in that: step a1 includes the following sub-steps:
substep A101, preparing a graphene oxide grafted dichlorostyrene monomer GO-ClSM;
substep A102, reducing a graphene oxide grafted dichlorostyrene monomer GO-ClSM to obtain a multilayer reduced graphene oxide grafted dichlorostyrene monomer RGO-ClSM;
and a substep A103, carrying out polymerization reaction on the multilayer reduced graphene oxide grafted dichlorostyrene monomer RGO-ClSM to obtain the multilayer reduced graphene oxide micro-sheet grafted polymer RGO-ClPS.
5. The method for dry-type alternate plating surface treatment of zinc alloy according to claim 4, characterized in that:
the substep a101 comprises: adding graphene oxide micro-sheets and dichlorostyrene into a solvent, and stirring and mixing; then adding silver chloride, and carrying out reflux reaction for 12-24h at the temperature of 50-80 ℃; after the reaction is finished, carrying out suction filtration, cleaning and vacuum drying to obtain a multilayer graphene oxide microchip grafted GO-ClSM monomer;
the substep A102 comprises the steps of adding the prepared GO-ClSM into a hydrazine hydrate solution, refluxing for 18 ~ 24h at the oil bath temperature of 100 ~ 140 ℃, filtering, cleaning and drying in vacuum after the reaction is finished, thus obtaining a multilayer reduced graphene oxide microchip grafted monomer, namely RGO-ClSM;
sub-step a103 comprises: and mixing the prepared RGO-ClSM monomer, divinylbenzene and ethylene glycol dimethacrylate, and then carrying out polymerization reaction to obtain the polymer RGO-ClPS grafted by the multilayer reduced graphene oxide micro-sheets.
6. The method for dry-type alternate plating surface treatment of zinc alloy according to claim 4, characterized in that: step a2 includes the following sub-steps:
substep A201, impregnating and compounding a polymer RGO-ClPS grafted by multilayer reduced graphene oxide micro-sheets and nano aluminum paste to obtain an RGO-ClPS impregnated by nano aluminum particles;
and a substep A202 of mixing the RGO-ClPS impregnated with the nano aluminum particles with a resin, an auxiliary agent and a solvent to obtain a pretreatment binding liquid.
7. The method for treating the dry-type generation electroplating surface of the zinc alloy according to claim 6, wherein the step A201 comprises the step of uniformly mixing RGO-ClPS, nano-aluminum paste, dimethyl amide and sodium dodecyl benzene sulfonate according to the weight ratio of 1:0.3 ~ 0.8.8: 2 ~ 4:0.05 ~ 0.2.2 at the temperature of 60-80 ℃ to obtain the RGO-ClPS impregnated with the nano-aluminum particles, wherein the particle size of the aluminum particles in the nano-aluminum paste is 5-100 nm.
8. The method for processing the surface of zinc alloy as claimed in claim 1, wherein the pre-processing binder comprises (by weight) RGO-ClPS 5 ~ 10 impregnated with nano-aluminum particles, resin 10 ~ 20%, adhesion promoter 0.5-3%, dispersant 0.3-2%, leveling agent 0.2-0.5%, and solvent in balance.
9. The method for dry-type alternate plating surface treatment of zinc alloy according to claim 8, characterized in that: the resin is one or a combination of more of polyamide, polyacrylate, epoxy resin, phenolic resin, polyurethane and chloroprene rubber; the adhesion promoter is one or more of silane coupling agent, chlorinated PP or phosphate functional monomer; the thickness of the pretreatment bonding layer is 2-5 μm.
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