CN108165958A - A kind of method of red copper surface chemical Ni-P plating-graphene composite deposite - Google Patents
A kind of method of red copper surface chemical Ni-P plating-graphene composite deposite Download PDFInfo
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- CN108165958A CN108165958A CN201810072041.XA CN201810072041A CN108165958A CN 108165958 A CN108165958 A CN 108165958A CN 201810072041 A CN201810072041 A CN 201810072041A CN 108165958 A CN108165958 A CN 108165958A
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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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
Abstract
The present invention provides a kind of method of red copper surface Electroless Plating Ni P graphene composite deposites, the method in the present invention carries out oil removing using the electrochemical deoiling liquid of consisting of：Sodium hydroxide：10~30g/L, sodium metasilicate：5~20g/L, sodium carbonate：10~30g/L, tertiary sodium phosphate：10~30g/L；Then chemical plating is carried out using the composite plating bath of following components：Nickel salt：20~50g/L, sodium hypophosphite：20~50g/L, sodium acetate：10~40g/L, malic acid：1~10g/L, lactic acid：5~20ml/L, surfactant：0.1~1.0g/L, Potassiumiodate：1~10mg/L, step A) in graphene oxide：0.1~2.0g/L.The Ni P graphenes composite deposite that red copper surface in the present invention is formed has more excellent corrosion resisting property and higher hardness.
Description
Technical field
The invention belongs to electroless plating technology field more particularly to a kind of red copper surface chemical Ni-P plating-graphene Composite Coatings
The method of layer.
Background technology
Technology of Chemical Composite Plating develops on the basis of original chemical plating, is added not during chemical plating
The solid particle of plating solution is dissolved in, it is allowed to be co-deposited to obtain the technology of composite deposite together with metal, referred to as chemically composited coating technology.
So far, has the composite deposite that related work person has developed variable grain, such as SiC, Al2O3、SiO2, diamond, carbon receives
Mitron etc..
Red copper due to good conductive, heat conductivility, having in industries such as electronics, machinery, chemical industry and widely applying, but
Since red copper surface is easily aoxidized, plating need to be carried out in red copper surface to improve the corrosion resisting property of red copper surface.Nickel phosphorus closes
Gold can improve the wear-resisting of copper surface, corrosion resisting property etc., but with the continuous improvement that people require coating performance, traditional nickel
Phosphor alloy coating cannot meet the needs of people, particularly with certain current Special use requirements.With nano material
With the continuous development of technology, there is the small size of the specificity such as power, heat, light, electricity, the nano structure superficial layer of functionalization can show
Writing improves the surface property of material.Therefore, it will be of great significance to the research of nickel phosphorus nano-composite plate.
Invention content
The purpose of the present invention is to provide a kind of method of red copper surface chemical Ni-P plating-graphene composite deposite, this hairs
The coating that method in bright obtains has excellent corrosion resisting property and higher hardness.
The present invention provides a kind of method of red copper surface chemical Ni-P plating-graphene composite deposite, includes the following steps：
A) concentrated nitric acid, the concentrated sulfuric acid and graphene are mixed, heating carries out oxidation reaction, obtains graphene oxide；
B) red copper is immersed in electrochemical deoiling liquid, oil removing is carried out, after then the sulfuric acid of use quality a concentration of 5% is to oil removing
Red copper carry out acid-wash activation；
The electrochemical deoiling liquid includes the component of following concentration：
Sodium hydroxide：10~30g/L, sodium metasilicate：5~20g/L, sodium carbonate：10~30g/L, tertiary sodium phosphate：10~30g/
L；
C) red copper after acid-wash activation is immersed in composite plating bath, inducing nickel plating using iron wire carries out, and takes out iron wire, carries out
Reaction, obtains Ni-P- graphene composite deposites；
The composite plating bath includes following components：
Nickel salt：20~50g/L, sodium hypophosphite：20~50g/L, sodium acetate：10~40g/L, malic acid：1~10g/L,
Lactic acid：5~20ml/L, surfactant：0.1~1.0g/L, Potassiumiodate：1~10mg/L, step A) in graphene oxide：
0.1~2.0g/L.
Preferably, the mass ratio of the volume of the concentrated nitric acid, the volume of the concentrated sulfuric acid and graphene is (20~40) mL：
10mL：(1~10) g.
Preferably, the temperature of the oxidation reaction is 50~70 DEG C；
The time of the oxidation reaction is 1~5 hour.
Preferably, the temperature of the oil removing is 30~80 DEG C；
The time of the oil removing is 3~5min.
Preferably, the electrochemical deoiling liquid includes following components：
Sodium hydroxide：20~30g/L, sodium metasilicate：10~20g/L, sodium carbonate：20~30g/L, tertiary sodium phosphate：20~
30g/L。
Preferably, in the composite plating bath, nickel salt is nickel sulfamic acid, nickel sulfate, nickel chloride, ortho phosphorous acid nickel and nitric acid
One or more of nickel.
Preferably, in the composite plating bath, surfactant is neopelex, lauryl sodium sulfate, different
One or more of sodium octyl sulfate.
Preferably, the composite plating bath includes following components：
Nickel salt：30~45g/L, sodium hypophosphite：25~40g/L, sodium acetate：15~30g/L, malic acid：5~10g/L,
Lactic acid：5~15ml/L, surfactant：0.1~0.5g/L, Potassiumiodate：1~5mg/L, step A) in graphene oxide：
0.1~1.0g/L；
The pH value of the composite plating bath is 4~8.
Preferably, the step C) in react temperature be 70~80 DEG C；
The step C) in react time be 30~60min.
Preferably, the step A) in graphene grain size be 10~50nm.
The present invention provides a kind of methods of red copper surface chemical Ni-P plating-graphene composite deposite, include the following steps：
A) concentrated nitric acid, the concentrated sulfuric acid and graphene are mixed, heating carries out oxidation reaction, obtains graphene oxide；B) by red copper immersionization
It learns in degreasing fluid, carries out oil removing, then the sulfuric acid of use quality a concentration of 5% carries out acid-wash activation to the red copper after oil removing；Institute
State the component that electrochemical deoiling liquid includes following concentration：Sodium hydroxide：10~30g/L, sodium metasilicate：5~20g/L, sodium carbonate：10~
30g/L, tertiary sodium phosphate：10~30g/L；C) red copper after acid-wash activation is immersed in composite plating bath, induces nickel plating using iron wire
It carries out, takes out iron wire, reacted, obtain Ni-P- graphene composite deposites；The composite plating bath includes following components：Nickel salt：
20~50g/L, sodium hypophosphite：20~50g/L, sodium acetate：10~40g/L, malic acid：1~10g/L, lactic acid：5~20ml/
L, surfactant：0.1~1.0g/L, Potassiumiodate：1~10mg/L, step A) in graphene oxide：0.1~2.0g/L.This
Nano-graphene particle is added in chemical plating fluid and carries out chemical plating, and red copper surface is first pre-processed by invention, simultaneously
Have adjusted plating solution composition so that red copper surface formed Ni-P- graphenes composite deposite have more excellent corrosion resisting property and
Higher hardness.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the scanning electron microscope diagram of Ni-P- graphene composite deposites that the embodiment of the present invention 1 obtains；
Fig. 2 is the EDS collection of illustrative plates of plating Ni-P- graphene composite deposites that the embodiment of the present invention 1 obtains；
Fig. 3 is to be not added with graphene under the Ni-P- graphenes composite deposite and the same terms that the embodiment of the present invention 1 obtains to obtain
Ni-P alloy layers Tafel curve figure；
Fig. 4 is to be not added with graphene under the Ni-P- graphenes composite deposite and the same terms that the embodiment of the present invention 2 obtains to obtain
Ni-P alloy layers Tafel curve figure.
Specific embodiment
The present invention provides a kind of method of red copper surface chemical Ni-P plating-graphene composite deposite, includes the following steps：
A) concentrated nitric acid, the concentrated sulfuric acid and graphene are mixed, heating carries out oxidation reaction, obtains graphene oxide；
B) red copper is immersed in electrochemical deoiling liquid, oil removing is carried out, after then the sulfuric acid of use quality a concentration of 5% is to oil removing
Red copper carry out acid-wash activation；
The electrochemical deoiling liquid includes the component of following concentration：
Sodium hydroxide：10~30g/L, sodium metasilicate：5~20g/L, sodium carbonate：10~30g/L, tertiary sodium phosphate：10~30g/
L；
C) red copper after acid-wash activation is immersed in composite plating bath, inducing nickel plating using iron wire carries out, and takes out iron wire, carries out
Reaction, obtains Ni-P- graphene composite deposites；
The composite plating bath includes following components：
Nickel salt：20~50g/L, sodium hypophosphite：20~50g/L, sodium acetate：10~40g/L, malic acid：1~10g/L,
Lactic acid：5~20ml/L, surfactant：0.1~1.0g/L, Potassiumiodate：1~10mg/L, step A) in graphene oxide：
0.1~2.0g/L.
The present invention is existing to mix concentrated nitric acid, the concentrated sulfuric acid and graphene, and heating stirring is reacted, then with largely going
Ionized water rinses, then is filtered, dry, obtains graphene oxide, for use.
The ratio of the concentrated nitric acid, the concentrated sulfuric acid and graphene is (20~40) mL：10mL：(1~10) g, preferably 30mL：
10mL：5g；The temperature of the heating is preferably 50~70 DEG C, more preferably 60 DEG C；The time of the reaction is preferably 1~5 small
When, more preferably 2~4 hours.
The grain size of the graphene is preferably 10~50nm, more preferably 20~40nm, most preferably 30nm.
It is of the invention that red copper is now preferably subjected to surface preparation, it is followed successively by coated abrasive working decontamination, electrochemical deoiling and pickling and lives
Change.
The coated abrasive working decontamination is using 400#With 1200#Sand paper successively polishes to the surface of copper sheet；
The electrochemical deoiling is to immerse copper sheet in electrochemical deoiling liquid, is carried out fuel-displaced；
The electrochemical deoiling liquid includes following components：
Sodium hydroxide：10~30g/L, preferably 20~30g/L, more preferably 25g/L；Sodium metasilicate：5~20g/L, preferably
For 10~20g/L, more preferably 15g/L；Sodium carbonate：10~30g/L, preferably 20~30g/L, more preferably 25g/L；Phosphoric acid
Trisodium：10~30g/L, preferably 20~30g/L, more preferably 25g/L.
The temperature of the electrochemical deoiling is preferably 30~80 DEG C, more preferably 40~70 DEG C, most preferably 50~60 DEG C；Institute
The time for stating electrochemical deoiling is preferably 3~5min, more preferably 4min.
The acid-wash activation uses mass concentration, and for 5% sulfuric acid, the time of acid-wash activation is preferably 1~3min.It is described
The purpose of acid-wash activation is the oxidation film in order to remove red copper surface.
In the present invention, without first between the preparation of the graphene oxide and the surface preparation of red copper the two steps
The limitation of sequence afterwards.
After completing to the surface preparation of red copper, the present invention immerses the red copper after acid-wash activation in composite plating bath, is used in combination
Iron wire, which induces nickel plating, to carry out, and then takes out iron wire, is reacted, obtains Ni-P- graphene composite deposites.
The composite plating bath includes following components：
Nickel salt：20~50g/L, preferably 30~45g/L, more preferably 35~40g/L；Sodium hypophosphite：20~50g/
L, preferably 25~40g/L, more preferably 30~35g/L；Sodium acetate：10~40g/L, preferably 15~30g/L, more preferably
20~25g/L；Malic acid：1~10g/L, preferably 5~10g/L, lactic acid：5~20ml/L, preferably 5~15mL/L, it is more excellent
It is selected as 10~15mL/L；Surfactant：0.1~1.0g/L, more preferably 0.1~0.5g/L, more preferably 0.2~0.3g/
L；Potassiumiodate：1~10mg/L, preferably 1~5mg/L, step A) in graphene oxide：0.1~2.0g/L, preferably 0.1
~1.0g/L.
The nickel salt is preferably nickel sulfamic acid, nickel sulfate, nickel chloride, ortho phosphorous acid nickel and one kind or several in nickel nitrate
Kind；The surfactant is neopelex, lauryl sodium sulfate, one kind in iso-octyl sodium sulphate or several
Kind.
The pH value of the composite plating bath is preferably 4~8, more preferably 5~7, most preferably 6.
The temperature of the chemical plating is preferably 70~80 DEG C, more preferably 75 DEG C；The time of the chemical plating is preferably 30
~60min, more preferably 40~50min.
The present invention provides a kind of methods of red copper surface chemical Ni-P plating-graphene composite deposite, include the following steps：
A) concentrated nitric acid, the concentrated sulfuric acid and graphene are mixed, heating carries out oxidation reaction, obtains graphene oxide；B) by red copper immersionization
It learns in degreasing fluid, carries out oil removing, then the sulfuric acid of use quality a concentration of 5% carries out acid-wash activation to the red copper after oil removing；Institute
State the component that electrochemical deoiling liquid includes following concentration：Sodium hydroxide：10~30g/L, sodium metasilicate：5~20g/L, sodium carbonate：10~
30g/L, tertiary sodium phosphate：10~30g/L；C) red copper after acid-wash activation is immersed in composite plating bath, induces nickel plating using iron wire
It carries out, takes out iron wire, reacted, obtain Ni-P- graphene composite deposites；The composite plating bath includes following components：Nickel salt：
20~50g/L, sodium hypophosphite：20~50g/L, sodium acetate：10~40g/L, malic acid：1~10g/L, lactic acid：5~20ml/
L, surfactant：0.1~1.0g/L, Potassiumiodate：1~10mg/L, step A) in graphene oxide：0.1~2.0g/L.This
Nano-graphene particle is added in chemical plating fluid and carries out chemical plating, and red copper surface is first pre-processed by invention, simultaneously
Have adjusted plating solution composition so that red copper surface formed Ni-P- graphenes composite deposite have more excellent corrosion resisting property and
Higher hardness.
In order to further illustrate the present invention, with reference to embodiments to one kind provided by the invention in red copper surface chemical plating
The method of Ni-P- graphene composite deposites is described in detail, but cannot be understood as limiting the scope of the present invention.
Embodiment 1
The oxidation processes of graphene：A, by concentrated nitric acid 30ml, concentrated sulfuric acid 10ml, graphene 5g, it is uniformly mixed that obtain A molten
Liquid；B, solution A is heated to 70 DEG C, stirs 2h, then rinsed with a large amount of deionized waters, then be filtered, it is dry, it is aoxidized
Graphene is for use.
The pretreatment of red copper surface：C, by copper sheet through 400#With 1200#Sand paper polishes decontamination successively；D, by sodium hydroxide
A concentration of 20g/L, a concentration of 5g/L of sodium metasilicate, a concentration of 10g/L of sodium carbonate, tertiary sodium phosphate a concentration of 25g/L
Sodium hydroxide, sodium metasilicate, sodium carbonate, tertiary sodium phosphate are added in deionized water, are uniformly mixed, obtain electrochemical deoiling liquid by ratio
B；E, copper sheet is dipped in the B solution that temperature is 70 DEG C, oil removing 5min；It f, will with the sulfuric acid solution that mass percent is 5%
Copper sheet acid-wash activation 1min after oil removing.
The preparation of composite deposite：G, by a concentration of 25g/L of nickel salt, a concentration of 25g/L of sodium hypophosphite, sodium acetate
A concentration of 10g/L, a concentration of 5g/L of malic acid, lactic acid concn 8ml/L, surfactant iso-octyl sodium sulphate and dodecane
A concentration of 0.2g/L of base benzene sulfonic acid sodium salt, a concentration of 1mg/L of Potassiumiodate, graphene 0.6g/L, and it is 5 to adjust pH value, is obtained
Ni-P- graphene composite plating baths C；H, step 2 copper sheet after pretreatment is immersed in 80 DEG C of C solution, and uses iron wire
After inducing nickel plating progress, iron wire is taken out, 30min is reacted, completes the preparation of composite deposite.
Electronic Speculum observation is scanned to the composite deposite that the embodiment of the present invention 1 obtains, test result is as shown in Figure 1, by Fig. 1
With Fig. 2 it is found that the graphene particles distribution uniform of red copper surface, and it is successfully realized the deposition of graphene.
Tafel curve test, test are carried out using the PGSTAT302N types electrochemical workstation of Wan Tong companies of Switzerland production
The Tafel curve of Ni-P- graphene composite deposites that the embodiment of the present invention 1 obtains, test result is as shown in figure 3, Fig. 3 is this
The Ni-P alloy layers that graphene obtains are not added under Ni-P- graphenes composite deposite and the same terms that inventive embodiments 1 obtain
Tafel curve.From the figure 3, it may be seen that the corrosion electric current density of Ni-P- graphene composite deposites that the embodiment of the present invention 1 obtains is more
It is small, there is superior corrosion resisting property than simple Ni-P alloy layers.
The X-1000 micro Vickers that Instrument Ltd.'s production is learned by upper Haitai Mingguang City measures present invention implementation
The hardness of Ni-P- graphene composite deposites that example obtains is 658Hv, and the hardness of simple Ni-P alloy layers is only 228Hv, can
To find out that Ni-P- graphene composite deposite hardness is greatly improved.
Embodiment 2
According to method described in embodiment 1 in red copper surface chemical Ni-P plating-graphene composite deposite, with embodiment 1
Difference lies according to a concentration of 40g/L of nickel salt, a concentration of 30g/L of sodium hypophosphite, a concentration of 20g/L of sodium acetate, apple
A concentration of 10g/L of tartaric acid, lactic acid concn 16ml/L, surfactant iso-octyl sodium sulphate and neopelex
A concentration of 0.3g/L, a concentration of 2mg/L of Potassiumiodate, graphene 0.4g/L are prepared, and adjust pH value to 4.5.
According to the method for embodiment 1, the Ta Feier of Ni-P- graphene composite deposites that the embodiment of the present invention 2 obtains is tested
Curve, test result is as shown in figure 4, as can be seen from FIG. 4, the Ni-P- graphene composite deposites that embodiment 2 obtains are than simple
Ni-P alloy layers have better corrosion resisting property.
The hardness of Ni-P- graphene composite deposites obtained by the microhardness testers measurement embodiment of the present invention is 643Hv,
And the hardness of simple Ni-P alloy layers is only 198Hv, it can be seen that Ni-P- graphene composite deposite hardness is greatly carried
It rises.
Embodiment 3
According to method described in embodiment 1 in red copper surface chemical Ni-P plating-graphene composite deposite, with embodiment 1
Difference lies in, electrochemical deoiling liquid according to a concentration of 30g/L of sodium hydroxide, a concentration of 10g/L of sodium metasilicate, sodium carbonate concentration
A concentration of 35g/L for 10g/L, tertiary sodium phosphate is prepared.
According to the method for embodiment 1, the Tafel curve of 3 obtained composite deposite of the embodiment of the present invention, test are tested
As a result it is that the Ni-P- graphenes composite deposite that embodiment 3 obtains has superior corrosion resistance than simple Ni-P alloy layers
It can be with higher hardness
Comparative example 1
According to method described in embodiment 1 in red copper surface chemical Ni-P plating-graphene composite deposite, the difference is that, than
Compared with the sodium hydroxide solution that the electrochemical deoiling liquid in example 1 uses 25g/L.
The corrosion electric current density i of the Ni-P- graphene composite deposites obtained obtained by comparative example 1corr=9.237 × 10- 6A/cm2, hence it is evident that more than the corrosion electric current density in embodiment 1, so corrosion resisting property is worse；Secondly comparative example 1 obtains compound
Coating, hardness 528Hv, less than the hardness of the composite deposite of embodiment 1.
Comparative example 2
According to method described in embodiment 1 in red copper surface chemical Ni-P plating-graphene composite deposite, the difference is that, than
It is replaced compared with the surfactant in composite plating bath in example 2 using the compound stabilizer that thiocarbamide, Potassiumiodate and potassium iodide form.
The corrosion electric current density i of the Ni-P- graphene composite deposites obtained obtained by comparative example 2corr=8.752 × 10- 6A/cm2, hence it is evident that more than the corrosion electric current density in embodiment 1, so corrosion resisting property is worse；Secondly comparative example 1 obtains compound
Coating, hardness 589Hv, less than the hardness of the composite deposite of embodiment 1.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method of red copper surface chemical Ni-P plating-graphene composite deposite, includes the following steps：
A) concentrated nitric acid, the concentrated sulfuric acid and graphene are mixed, heating carries out oxidation reaction, obtains graphene oxide；
B) red copper is immersed in electrochemical deoiling liquid, carries out oil removing, then the sulfuric acid of use quality a concentration of 5% is to the purple after oil removing
Copper carries out acid-wash activation；
The electrochemical deoiling liquid includes the component of following concentration：
Sodium hydroxide：10~30g/L, sodium metasilicate：5~20g/L, sodium carbonate：10~30g/L, tertiary sodium phosphate：10~30g/L；
C) red copper after acid-wash activation is immersed in composite plating bath, inducing nickel plating using iron wire carries out, and takes out iron wire, carries out anti-
Should, obtain Ni-P- graphene composite deposites；
The composite plating bath includes following components：
Nickel salt：20~50g/L, sodium hypophosphite：20~50g/L, sodium acetate：10~40g/L, malic acid：1~10g/L, breast
Acid：5~20ml/L, surfactant：0.1~1.0g/L, Potassiumiodate：1~10mg/L, step A) in graphene oxide：0.1
~2.0g/L.
2. according to the method described in claim 1, it is characterized in that, the volume of the concentrated nitric acid, the volume of the concentrated sulfuric acid and graphite
The mass ratio of alkene is (20~40) mL：10mL：(1~10) g.
3. according to the method described in claim 1, it is characterized in that, the temperature of the oxidation reaction is 50~70 DEG C；
The time of the oxidation reaction is 1~5 hour.
4. according to the method described in claim 1, it is characterized in that, the temperature of the oil removing is 30~80 DEG C；
The time of the oil removing is 3~5min.
5. according to the method described in claim 1, it is characterized in that, the electrochemical deoiling liquid includes following components：
Sodium hydroxide：20~30g/L, sodium metasilicate：10~20g/L, sodium carbonate：20~30g/L, tertiary sodium phosphate：20~30g/L.
6. according to the method described in claim 1, it is characterized in that, in the composite plating bath, nickel salt is nickel sulfamic acid, sulfuric acid
One or more of nickel, nickel chloride, ortho phosphorous acid nickel and nickel nitrate.
7. according to the method described in claim 1, it is characterized in that, in the composite plating bath, surfactant is dodecyl
One or more of benzene sulfonic acid sodium salt, lauryl sodium sulfate, iso-octyl sodium sulphate.
8. according to the method described in claim 1, it is characterized in that, the composite plating bath includes following components：
Nickel salt：30~45g/L, sodium hypophosphite：25~40g/L, sodium acetate：15~30g/L, malic acid：5~10g/L, breast
Acid：5~15ml/L, surfactant：0.1~0.5g/L, Potassiumiodate：1~5mg/L, step A) in graphene oxide：0.1
~1.0g/L；
The pH value of the composite plating bath is 4~8.
9. according to the method described in claim 1, the it is characterized in that, step C) in the temperature reacted be 70~80 DEG C；
The step C) in react time be 30~60min.
10. according to the method described in claim 1, the it is characterized in that, step A) in the grain size of graphene be 10~50nm.
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| CN201810072041.XA CN108165958A (en) | 2018-01-25 | 2018-01-25 | A kind of method of red copper surface chemical Ni-P plating-graphene composite deposite |
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| CN201810072041.XA CN108165958A (en) | 2018-01-25 | 2018-01-25 | A kind of method of red copper surface chemical Ni-P plating-graphene composite deposite |
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| CN112251739A (en) * | 2020-10-23 | 2021-01-22 | 哈尔滨工业大学 | Aluminum-induced chemical plating method for pre-plating copper film |
| CN112382878A (en) * | 2020-11-04 | 2021-02-19 | 贵州航天电器股份有限公司 | Jack assembly with composite coating, electric connector and electroplating method thereof |
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