CN109972124A - A method of copper-graphite alkene composite deposite is prepared on ABS plastic surface - Google Patents

A method of copper-graphite alkene composite deposite is prepared on ABS plastic surface Download PDF

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Publication number
CN109972124A
CN109972124A CN201910323023.9A CN201910323023A CN109972124A CN 109972124 A CN109972124 A CN 109972124A CN 201910323023 A CN201910323023 A CN 201910323023A CN 109972124 A CN109972124 A CN 109972124A
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China
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abs plastic
graphite alkene
copper
composite deposite
plastic surface
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康志新
杨松潭
郭涛
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN201910323023.9A priority Critical patent/CN109972124A/en
Publication of CN109972124A publication Critical patent/CN109972124A/en
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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
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • 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
    • C23C18/42—Coating with noble metals
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Abstract

The invention belongs to material surface engineering technolog fields, disclose a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface.ABS plastic is added to progress chemical pre-plating silver processing in chemical plating liquid after pretreatment, is then added in the electroplate liquid being made by copper sulphate, the concentrated sulfuric acid, graphene and water and carries out electroplating processes, prepare copper-graphite alkene composite deposite on ABS plastic surface.Present method avoids the use of chromic acid and colloid palladium, have the advantages that pollute small, at low cost, simple process.Prepared composite deposite even compact, and there is superior electrical conductivity and wear-resisting property, widen the application field of copper electroplating layer.

Description

A method of copper-graphite alkene composite deposite is prepared on ABS plastic surface
Technical field
The invention belongs to material surface engineering technolog fields, and in particular to one kind prepares copper-graphite alkene on ABS plastic surface The method of composite deposite.
Background technique
Plastic material is obtained in daily production and life due to its good chemical stability and excellent processing performance It is widely applied.Metallization of plastic surface, had both combined that plastics itself rigidity is big, and density is small, excellent comprehensive such as intensity height Can, while the performance of institute's plating metal is combined again, such as electric conductivity, wearability, magnetic conductivity and decorative performance.Thus this technology It has received widespread attention and in-depth study, and achieves rapid development, and be widely used in printed circuit board, micro- The fields such as electronic technology, electrochemical protection, decorative coveringn and shield technology.
Acrylonitrile-butadiene-styrene copolymer is also known as ABS, be it is most widely used can chemical metallization engineering plastics. ABS plastic itself does not have electric conductivity, and directly it can not be electroplated, and need to pass through a series of pre-treating technology, formation can The conductive layer of plating could prepare the coat of metal.Pre-treating technology specifically includes that roughening treatment, sensitized treatment, activation processing Deng.But this process route very complicated, and due to strong oxidizers such as the process chromic acid, the sulfuric acid that use of roughening etching, Biggish pollution can be brought to industrial environment.Meanwhile traditional industry is to make plastics be able to carry out subsequent chemical plating, greatly Palladium is mostly used to be activated, it is with high costs, and be mainly mechanical anchor, the coating knot finally prepared between the coat of metal and plastics Resultant force can not be ensured effectively.
The coating of traditional copper-plating technique preparation easily tarnishes in humid air, acts on carbon dioxide or chloride, One layer of basic copper carbonate of Surface Creation or chlorination copper film layer.The corrosion resistance of copper is poor, and electro-coppering is generally only used as many The transition zone or middle layer of coating, cannot be used alone.Graphene is the novel carbon materials with excellent properties risen in recent years Material, intensity is high, has excellent corrosion resistance, electric conductivity, self-lubricating property, can be used as in particle incorporation composite deposite.
In conclusion defect in view of the prior art, it is accordingly required in particular to a kind of technique for preparing composite deposite is developed, to solve The deficiencies in the prior art.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the purpose of the present invention is to provide one kind to mould in ABS The method that material surface prepares copper-graphite alkene composite deposite.Inventive process avoids the uses of chromic acid and colloid palladium, have pollution The advantages of small, at low cost, simple process, and prepare the composite deposite for having superior electrical conductivity and wear-resisting property.
The object of the invention is achieved through the following technical solutions:
A method of copper-graphite alkene composite deposite, including following preparation step are prepared on ABS plastic surface:
ABS plastic is added to in chemical plating liquid progress chemical pre-plating silver processing after pretreatment, be then added to by Electroplating processes are carried out in the electroplate liquid that copper sulphate, the concentrated sulfuric acid, graphene and water are made into, and prepare copper-graphite alkene on ABS plastic surface Composite deposite.
Further, the pretreatment, which refers to, successively carries out vacuum heat-preserving processing (removal internal stress), alkali cleaning for ABS plastic Oil removal treatment, silane coupler modified processing and sensitized treatment.
Further, the temperature of the vacuum heat-preserving processing is 50~70 DEG C, and the time is 2~4h.
Further, the alkali cleaning oil removal treatment refers to that in the concentration of sodium hydroxide be 30~70g/L, the concentration of sodium carbonate For in the alkali cleaning degreasing fluid of 5~20g/L at a temperature of 20~30 DEG C 1~2h of immersion treatment.
Further, the silane coupler modified processing, which refers to, is containing azido silanes coupling agent and mercaptan base silane In the aqueous solution of coupling agent at a temperature of 20~30 DEG C 10~15min of immersion treatment.
Further, the sensitized treatment refer to the stannous chloride and concentration that concentration is 20~50g/L be 10~ The 37wt% hydrochloric acid of 50ml/L, in the sensitizing solution of mixed configuration at a temperature of 20~30 DEG C 20~30min of immersion treatment.
Further, the chemical plating liquid refers to the aqueous solution containing silver nitrate, ammonium hydroxide, glyoxal and triethanolamine； The concentration of silver nitrate is 15~25g/L in the chemical plating liquid, and the concentration of ammonium hydroxide is 10~20ml/L, and the concentration of glyoxal is 50~70ml/L, the concentration of triethanolamine are 10~20ml/L.
Further, chemical pre-plating silver treated ABS plastic is rinsed with 80~90 DEG C of deionized water, It is rinsed drying with dehydrated alcohol again, is put into 70~80 DEG C of vacuum ovens after keeping the temperature 30~60min and takes out for use.
Further, in the electroplate liquid each ingredient concentration be 150~250g/L of copper sulphate, the 98wt% concentrated sulfuric acid 40~ 60g/L, 0.5~2g/L of graphene, solvent are distilled water.
Further, the temperature of the electroplating processes is 20~30 DEG C, and current density is 0.5~2.0A/dm2, when plating Between be 10~40min.
Further, drying further is rinsed with distilled water and dehydrated alcohol after the completion of the electroplating processes, it is put into 50~ Dry 1~2h in 70 DEG C of vacuum oven.
Compared with the existing technology, method of the invention have the following advantages that and the utility model has the advantages that
(1) a kind of method treatment process for preparing copper-graphite alkene composite deposite on ABS plastic surface of the invention is easy to real Existing, simple process optimizes cumbersome conventional process flow.
(2) electroplating pretreatment process that method of the invention uses avoids the use of chromic acid and colloid palladium, reduces to ring The pollution in border reduces production cost.
(3) composite deposite even compact prepared by method of the invention has superior electrical conductivity and wear-resisting property, widens The application field of copper electroplating layer.
Detailed description of the invention
Fig. 1 is the pictorial diagram of the ABS plastic surface copper-graphite alkene composite deposite of Examples 1 to 3 preparation；Wherein (a) is real The pictorial diagram of the composite deposite of example 1 is applied, is (b) pictorial diagram of the composite deposite of embodiment 2, (c) is the composite deposite of embodiment 3 Pictorial diagram.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the copper-graphite alkene composite deposite of Examples 1 to 3 preparation；Wherein (a) is to implement The SEM of the composite deposite of example 1 schemes, wherein (b) scheming for the SEM of the composite deposite of embodiment 2, wherein (c) being the compound of embodiment 3 The SEM of coating schemes.
Fig. 3 is the Raman spectrogram of copper-graphite alkene composite deposite prepared by embodiment 1.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited In this.
Embodiment 1
A kind of method preparing copper-graphite alkene composite deposite on ABS plastic surface of the present embodiment, concrete operation step is such as Under:
Step 1: ABS plastic is placed in a vacuum drying oven removal internal stress
ABS plastic is put into the processing that internal stress is removed in vacuum oven, the temperature adjustment in vacuum oven It is 60 DEG C, keeps the temperature 2h.
Step 2: alkali cleaning oil removal treatment is carried out to the ABS plastic after isothermal holding
ABS plastic obtained in step 1 is placed in alkali cleaning degreasing fluid and impregnates 1h, temperature is 25 DEG C；With distillation after taking-up It is stand-by that water and dehydrated alcohol rinse drying；Alkali cleaning degreasing fluid is the mixed aqueous solution of 70g/L sodium hydroxide and 20g/L sodium carbonate.
Step 3: by after alkali cleaning oil removing ABS plastic organo silane coupling agent and sensitizing solution handle
ABS plastic obtained in step 2 is placed in organo silane coupling agent and impregnates 10min, organo silane coupling agent is Solution containing azido silanes coupling agent and mercapto silane coupling agent, temperature are 25 DEG C；With distilled water and anhydrous after taking-up Ethyl alcohol rinses drying, is put into sensitizing solution and impregnates 20min, and temperature is 25 DEG C；The concentration of each ingredient in sensitizing solution: stannous chloride Concentration is 20g/L, and the concentration of the hydrochloric acid of 37wt% is 10ml/L.
Step 4: by treated before menstruation, ABS plastic carries out the processing of chemical pre-plating silver
By treated before menstruation in step 3, ABS plastic carries out chemical pre-plating silver, and the concentration of silver nitrate is in silver plating solution 20g/L, the concentration of ammonium hydroxide are 15ml/L, and the concentration of glyoxal is 60ml/L, triethanolamine 15ml/L；It is pre- that silver-plated treated ABS plastic is rinsed with 80 DEG C of deionized water, then is rinsed drying with dehydrated alcohol, is put into vacuum oven and is kept the temperature It is taken out after 60min stand-by；The temperature of vacuum oven is 70 DEG C.
Step 5: the preparation of copper-graphite alkene electroplate liquid
Copper sulphate, the concentrated sulfuric acid and graphene are made by mixing electroplate liquid using solvent, the concentration of each ingredient is sulphur in solution Sour copper 220g/L, 98wt% concentrated sulfuric acid 60g/L, graphene 1g/L, solvent is distilled water.
Step 6: silver-plated pretreated ABS plastic is placed in electroplate liquid, electroplated postposition is protected in a vacuum drying oven It is taken out after temperature, copper-graphite alkene composite deposite is made on ABS plastic surface
By treated that ABS plastic is placed in the electroplate liquid of step 5 through step 4, it is put into magnetic rotor in electroplate liquid, puts It sets on magnetic stirring apparatus, connects DC power supply, be electroplated, electroplating time 20min, temperature is 25 DEG C, and current density is 1.0A/dm2；ABS plastic is taken out from electroplate liquid after plating, drying is rinsed with distilled water and dehydrated alcohol, it is dry to be put into vacuum Dry 1h in dry case, the temperature of vacuum oven are 60 DEG C；Copper-graphite alkene composite deposite is made on ABS plastic surface after taking-up.
Following detection characterization has been carried out to prepared ABS plastic surface copper-graphite alkene composite deposite:
(1) morphology analysis: morphology analysis is carried out to prepared copper-graphite alkene composite deposite, pictorial diagram is as shown in figure 1 (a) Shown, SEM figure, it can be seen that there is flake graphite alkene in coating in figure, is evenly distributed as shown in (a) in Fig. 2.
(2) constituent analysis, the Raman light of composite deposite constituent analysis: are carried out to prepared copper-graphite alkene composite deposite On composite deposite as shown in figure 3, there are the typical Raman signatures of graphene, respectively positioned at 1350cm in spectrogram-1The D of left and right Peak, 1584cm-1The peak G and 2722cm of left and right-1The left and right peak 2D, show to prepare copper-graphite alkene composite deposite.
Embodiment 2
A kind of method preparing copper-graphite alkene composite deposite on ABS plastic surface of the present embodiment, concrete operation step is such as Under:
Step 1: ABS plastic is placed in a vacuum drying oven removal internal stress
ABS plastic is put into the processing that internal stress is removed in vacuum oven, the temperature adjustment in vacuum oven It is 50 DEG C, keeps the temperature 3h.
Step 2: alkali cleaning oil removal treatment is carried out to the ABS plastic after isothermal holding
ABS plastic obtained in step 1 is placed in alkali cleaning degreasing fluid and impregnates 1.5h, temperature is 20 DEG C；With steaming after taking-up It is stand-by that distilled water and dehydrated alcohol rinse drying；Alkali cleaning degreasing fluid is water-soluble for the mixing of 50g/L sodium hydroxide and 10g/L sodium carbonate Liquid.
Step 3: by after alkali cleaning oil removing ABS plastic organo silane coupling agent and sensitizing solution handle
ABS plastic obtained in step 2 is placed in organo silane coupling agent and impregnates 15min, organo silane coupling agent is Solution containing azido silanes coupling agent and mercapto silane coupling agent, temperature are 20 DEG C；With distilled water and anhydrous after taking-up Ethyl alcohol rinses drying, is put into sensitizing solution and impregnates 25min, and temperature is 20 DEG C；The concentration of each ingredient in sensitizing solution: stannous chloride Concentration is 30g/L, and the concentration of the hydrochloric acid of 37wt% is 20ml/L.
Step 4: by treated before menstruation, ABS plastic carries out the processing of chemical pre-plating silver
By treated before menstruation in step 3, ABS plastic carries out chemical pre-plating silver, and the concentration of silver nitrate is in silver plating solution 25g/L, the concentration of ammonium hydroxide are 18ml/L, and the concentration of glyoxal is 65ml/L, triethanolamine 18ml/L；It is pre- that silver-plated treated ABS plastic is rinsed with 85 DEG C of deionized water, then is rinsed drying with dehydrated alcohol, is put into vacuum oven and is kept the temperature It is taken out after 50min stand-by；The temperature of vacuum oven is 75 DEG C.
Step 5: the preparation of copper-graphite alkene electroplate liquid
Copper sulphate, the concentrated sulfuric acid and graphene are made by mixing electroplate liquid using solvent, the concentration of each ingredient is sulphur in solution Sour copper 250g/L, 98wt% concentrated sulfuric acid 50g/L, graphene 1.5g/L, solvent is distilled water.
Step 6: silver-plated pretreated ABS plastic is placed in electroplate liquid, electroplated postposition is protected in a vacuum drying oven It is taken out after temperature, copper-graphite alkene composite deposite is made on ABS plastic surface
By treated that ABS plastic is placed in the electroplate liquid of step 5 through step 4, it is put into magnetic rotor in electroplate liquid, puts It sets on magnetic stirring apparatus, connects DC power supply, be electroplated, electroplating time 40min, temperature is 30 DEG C, and current density is 2.0A/dm2；ABS plastic is taken out from electroplate liquid after plating, drying is rinsed with distilled water and dehydrated alcohol, it is dry to be put into vacuum Dry 2h in dry case, the temperature of vacuum oven are 70 DEG C；Copper-graphite alkene composite deposite is made on ABS plastic surface after taking-up.
Following detection characterization has been carried out to prepared ABS plastic surface copper-graphite alkene composite deposite:
Morphology analysis: carrying out morphology analysis to prepared copper-graphite alkene composite deposite, pictorial diagram (b) institute as shown in figure 1 Show, SEM figure, it can be seen that there is flake graphite alkene in coating in figure, is evenly distributed as shown in (b) in Fig. 2.
Embodiment 3
A kind of method preparing copper-graphite alkene composite deposite on ABS plastic surface of the present embodiment, concrete operation step is such as Under:
Step 1: ABS plastic is placed in a vacuum drying oven removal internal stress
ABS plastic is put into the processing that internal stress is removed in vacuum oven, the temperature adjustment in vacuum oven It is 70 DEG C, keeps the temperature 4h.
Step 2: alkali cleaning oil removal treatment is carried out to the ABS plastic after isothermal holding
ABS plastic obtained in step 1 is placed in alkali cleaning degreasing fluid and impregnates 2h, temperature is 30 DEG C；With distillation after taking-up It is stand-by that water and dehydrated alcohol rinse drying；Alkali cleaning degreasing fluid is the mixed aqueous solution of 60g/L sodium hydroxide and 15g/L sodium carbonate.
Step 3: by after alkali cleaning oil removing ABS plastic organo silane coupling agent and sensitizing solution handle
ABS plastic obtained in step 2 is placed in organo silane coupling agent and impregnates 12min, organo silane coupling agent is Solution containing azido silanes coupling agent and mercapto silane coupling agent, temperature are 30 DEG C；With distilled water and anhydrous after taking-up Ethyl alcohol rinses drying, is put into sensitizing solution and impregnates 25min, and temperature is 30 DEG C；The concentration of each ingredient in sensitizing solution: stannous chloride Concentration is 50g/L, and the concentration of the hydrochloric acid of 37wt% is 30ml/L；
Step 4: by treated before menstruation, ABS plastic carries out the processing of chemical pre-plating silver
By treated before menstruation in step 3, ABS plastic carries out chemical pre-plating silver, and the concentration of silver nitrate is in silver plating solution 15g/L, the concentration of ammonium hydroxide are 20ml/L, and the concentration of glyoxal is 70ml/L, triethanolamine 20ml/L；It is pre- that silver-plated treated ABS plastic is rinsed with 90 DEG C of deionized water, then is rinsed drying with dehydrated alcohol, is put into vacuum oven and is kept the temperature It is taken out after 40min stand-by；The temperature of vacuum oven is 80 DEG C.
Step 5: the preparation of copper-graphite alkene electroplate liquid
Copper sulphate, the concentrated sulfuric acid and graphene are made by mixing electroplate liquid using solvent, the concentration of each ingredient is sulphur in solution Sour copper 150g/L, 98wt% concentrated sulfuric acid 40g/L, graphene 0.5g/L, solvent is distilled water.
Step 6: silver-plated pretreated ABS plastic is placed in electroplate liquid, electroplated postposition is protected in a vacuum drying oven It is taken out after temperature, copper-graphite alkene composite deposite is made on ABS plastic surface
By treated that ABS plastic is placed in the electroplate liquid of step 5 through step 4, it is put into magnetic rotor in electroplate liquid, puts It sets on magnetic stirring apparatus, connects DC power supply, be electroplated, electroplating time 10min, temperature is 20 DEG C, and current density is 0.5A/dm2；ABS plastic is taken out from electroplate liquid after plating, drying is rinsed with distilled water and dehydrated alcohol, it is dry to be put into vacuum Dry 1.5h in dry case, the temperature of vacuum oven are 50 DEG C；Copper-graphite alkene Composite Coatings are made on ABS plastic surface after taking-up Layer.
Following detection characterization has been carried out to prepared ABS plastic surface copper-graphite alkene composite deposite:
Morphology analysis: carrying out morphology analysis to prepared copper-graphite alkene composite deposite, pictorial diagram (c) institute as shown in figure 1 Show, SEM figure, it can be seen that there is flake graphite alkene in coating in figure, is evenly distributed as shown in (c) in Fig. 2.
It can be seen by the result to the morphology analysis of copper-graphite alkene composite deposite prepared by above embodiments 1~3 Out, occur flake graphite alkene in coating, be evenly distributed；And with the increase of current density, graphene concentration, electroplating time, Graphene quantity in composite deposite gradually increases.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface, it is characterised in that including preparing step as follows It is rapid:
ABS plastic is added to progress chemical pre-plating silver processing in chemical plating liquid after pretreatment, is then added to by sulfuric acid Electroplating processes are carried out in the electroplate liquid that copper, the concentrated sulfuric acid, graphene and water are made into, it is compound to prepare copper-graphite alkene on ABS plastic surface Coating.
2. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 1, feature Be: the pretreatment, which refers to, successively carries out vacuum heat-preserving processing, alkali cleaning oil removal treatment, silane coupler modified for ABS plastic Processing and sensitized treatment.
3. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 2, feature Be: the temperature of the vacuum heat-preserving processing is 50~70 DEG C, and the time is 2~4h；The alkali cleaning oil removal treatment refers in hydrogen-oxygen The concentration for changing sodium is 30~70g/L, is soaked at a temperature of 20~30 DEG C in the alkali cleaning degreasing fluid that the concentration of sodium carbonate is 5~20g/L 1~2h of bubble processing.
4. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 2, feature Be: the silane coupler modified processing refers to water-soluble containing azido silanes coupling agent and mercapto silane coupling agent In liquid at a temperature of 20~30 DEG C 10~15min of immersion treatment.
5. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 2, feature Be: the sensitized treatment refers in the stannous chloride that concentration is 20~50g/L and 37wt% salt that concentration is 10~50ml/L Acid, in the sensitizing solution of mixed configuration at a temperature of 20~30 DEG C 20~30min of immersion treatment.
6. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 1, feature Be: the chemical plating liquid refers to the aqueous solution containing silver nitrate, ammonium hydroxide, glyoxal and triethanolamine；The chemical silvering The concentration of silver nitrate is 15~25g/L in liquid, and the concentration of ammonium hydroxide is 10~20ml/L, and the concentration of glyoxal is 50~70ml/L, The concentration of triethanolamine is 10~20ml/L.
7. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 1, feature Be: treated that ABS plastic is further rinsed with 80~90 DEG C of deionized water for chemical pre-plating silver, then with anhydrous Ethyl alcohol is rinsed drying, is put into 70~80 DEG C of vacuum ovens after keeping the temperature 30~60min and takes out for use.
8. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 1, feature Be: the concentration of each ingredient is 150~250g/L of copper sulphate, 40~60g/L of the 98wt% concentrated sulfuric acid, graphene in the electroplate liquid 0.5~2g/L, solvent are distilled water.
9. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 8, feature Be: the temperature of the electroplating processes is 20~30 DEG C, and current density is 0.5~2.0A/dm2, electroplating time be 10~ 40min。
10. a kind of method for preparing copper-graphite alkene composite deposite on ABS plastic surface according to claim 1, feature It is: further rinses drying with distilled water and dehydrated alcohol after the completion of the electroplating processes, it is dry is put into 50~70 DEG C of vacuum Dry 1~2h in dry case.
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