CN107916415A - The preparation method of graphene phosphatization nickel composite deposite and the coating being prepared - Google Patents
The preparation method of graphene phosphatization nickel composite deposite and the coating being prepared Download PDFInfo
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- CN107916415A CN107916415A CN201711167768.8A CN201711167768A CN107916415A CN 107916415 A CN107916415 A CN 107916415A CN 201711167768 A CN201711167768 A CN 201711167768A CN 107916415 A CN107916415 A CN 107916415A
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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
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
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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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
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Abstract
The present invention relates to composite deposite technical field, a kind of preparation method in particular to graphene phosphatization nickel composite deposite and the coating being prepared, the preparation method of the graphene phosphatization nickel composite deposite, includes the following steps：Graphene ultrasonic disperse is obtained into composite plating bath in phosphatization nickel plating bath, then the matrix of pretreatment is placed in composite plating bath and carries out ultrasonic plating.Present invention introduces ultrasound and surfactant, during composite plating bath and plating is prepared, graphene can be made fully dispersed, effectively prevents the reunion of graphene；Micro-bubble in plating solution vibrates under the action of ultrasonic wave, and grow focused energy, bubble collapse releases energy when reaching threshold value, produce localized hyperthermia's high pressure, promote the uniform mixing between each reactant in composite plating bath, accelerate the diffusion of reactant and product, promote solid New phase formation, improve the deposition velocity of composite deposite.
Description
Technical field
The present invention relates to composite deposite technical field, in particular to a kind of system of graphene-phosphatization nickel composite deposite
Preparation Method and the coating being prepared.
Background technology
Chemical plating nickel phosphide (Ni-P) coating is due to possessing higher hardness, good corrosion resistance and wearability, in mould
It is widely used in tool material.In recent years, graphene has obtained more and more concerns in the composite, by graphite
Alkene is mutually added to the comprehensive performance for being conducive to improve composite deposite in nickel phosphide (Ni-P) coating as enhancing.
In existing graphene-nickel phosphide (G-Ni-P) composite deposite preparation scheme, the coating of chemical plating method preparation
Due to obtaining the favor of researcher with higher surface quality and good combination power.Since graphene is with very high
Specific surface area and surface energy, easily reunite in the solution, influence the uniformity of composite deposite.In order to improve graphene in the plating solution
Dispersion performance, researcher is adding alcohol family macromolecule surfactant and using by way of magnetic agitation, making graphene
It is dispersed in the plating solution.But during magnetic agitation, graphene is easily adhered to for its surface energy of spontaneous reduction
In magnetic stir bar.Also, during chemical plating, continual magnetic agitation can also increase the disturbance of plating solution, increaseization
Learn the complexity of plating appts and the unstability of electroless plating reaction.
Since graphene oxide (GO) contains carboxyl and phenolic hydroxyl group, it can be ionized when disperseing in the solution, make graphene oxide
Surface is negatively charged, and producing electrostatic repulsion makes its stable dispersion in the solution.Therefore researcher first passes through chemical plating
Graphene oxide-nickel phosphide (GO-Ni-P) is obtained, then graphene oxide is reduced to by graphene by sodium borohydride reduction agent,
So as to which graphene-nickel phosphide (G-Ni-P) composite deposite be prepared.But during redox graphene, use
Different reducing agents are different to the reducing degree of graphene oxide, and poor controllability, strong influence composite deposite it is comprehensive
Energy.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is the preparation method for providing a kind of graphene-phosphatization nickel composite deposite, and described answers
Close the preparation method of coating disperses graphene uniform by ultrasonic wave added, and during chemical plating, ultrasonic cavitation is made
With the deposition velocity for improving coating, the needle pore defect of coating surface is effectively improved, makes the knot of composite deposite being prepared
Structure is finer and close.
The second object of the present invention is that providing a kind of preparation method of the graphene-phosphatization nickel composite deposite prepares
Obtained composite deposite, the composite deposite surface are evenly distributed, and coating structure is fine and close.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
The preparation method of graphene-phosphatization nickel composite deposite, includes the following steps：
Graphene ultrasonic disperse is obtained into composite plating bath in phosphatization nickel plating bath, then the matrix of pretreatment is placed in Composite Coatings
Ultrasonic plating is carried out in liquid.
The present invention graphene-phosphatization nickel composite deposite preparation method, by introduce ultrasound and surfactant, with
During composite plating bath processed, the micro-bubble in plating solution vibrates under the action of ultrasonic wave, and grows focused energy, reaches
Bubble collapse releases energy during threshold value, produces localized hyperthermia's high pressure, promotes the uniform mixing between each reactant in composite plating bath,
Graphene can be made fully dispersed, can effectively prevent the reunion of graphene, the otherwise reunion of graphene influences coating comprehensive performance；
And during plating, while ensureing that graphene is fully dispersed, ultrasonic wave produces localized hyperthermia's high pressure in composite plating bath,
Promote the uniform mixing between each reactant in composite plating bath, accelerate the diffusion of reactant and product, promote the shape of solid cenotype
Into so as to improve the deposition velocity of composite deposite.In addition, the effective pin hole and bubble for improving coating surface of the introducing of ultrasound
Defect, makes coating structure finer and close.
Compared to magnetic agitation of the prior art improve graphene dispersion mode, preparation method of the invention due to
Without using magnetic agitation, graphene will not be made largely to be adhered in magnetic stir bar, and composite plating bath will not be formed and disturbed.
Compared to the mode of redox graphene, preparation method of the invention is reproducible without reduction process, and be prepared
Composite deposite is evenly distributed.
Preferably, the plating under circular gap ultrasound condition.It is furthermore preferred that plating includes under circular gap ultrasound condition：
The matrix of pretreatment is placed in preplating in composite plating bath, then the plating 0.5-3h under circular gap ultrasound condition.It is further excellent
Choosing, the circular gap ultrasound condition is single ultrasound 0.5-3min, interval 5-15min.That is after ultrasound 0.5-3min, stop
It is only ultrasonic, ultrasound is then turned on after 5-15min, circulation carries out.Preferably, single ultrasound 1min, interval 10min.
Plating time cannot be long, in the range of above-mentioned plating time, can avoid during plating that temperature is excessive to be caused to stone
Black alkene disperses detrimental effect.In this plating time, the thickness of obtained coating is 10-50 μm, advantageously ensures that coating
Uniformity, and meet subsequent mechanical processing requirement.
Also, continuous ultrasound can influence adhesion of the nickel ion in solution in catalysis matrix surface, attachment difficulty increases,
Influence the deposition of phosphorus and nickel；Using the working method of interval ultrasound, it can ensure that nickel ion is attached to matrix surface and is reduced.
Preferably, ultrasonic frequency during plating is 35-45kHz.It is furthermore preferred that the ultrasonic frequency during plating is
40kHz。
Preferably, ultrasonic frequency during ultrasonic disperse is 35-45kHz.It is furthermore preferred that the ultrasound during ultrasonic disperse
Frequency be 40kHz.
Preferably, plating is carried out under the conditions of 70-90 DEG C.It is furthermore preferred that composite plating bath and matrix are carried out before plating pre-
Heat, is preheated to 70-90 DEG C.
Preferably, the graphene includes the graphene microchip of 1-5 layers of the number of plies.It is furthermore preferred that the graphene is to pass through
What the method for electrochemical stripping was prepared.It is further preferred that graphite flake is placed in positive pole, platinum electrode is placed in power supply
Anode, is dipped in the magnitude of voltage for changing application in electrolyte and voltage action time, and stripping obtains the graphene.
Preferably, the composite plating bath includes nickel salt, hypophosphite, complexing agent, surfactant and graphene.More
Preferably, stabilizer is further included in the composite plating bath.
Preferably, the nickel salt includes one or both of nickel sulfate and nickel chloride；The hypophosphite includes secondary
Sodium phosphite；The complexing agent includes one or both of lactic acid and propionic acid；The surfactant includes dodecyl sulphur
One or both of sour sodium and sodium taurocholate；The stabilizer includes thiocarbamide.
Preferably, the concentration of nickel salt is 0.05-0.15mol/L in the composite plating bath, and the concentration of hypophosphite is
0.1-0.3mol/L, the concentration of complexing agent are 0.1-0.5mol/L, and the concentration of surfactant is 0.001-0.01mol/L, stone
The concentration of black alkene is 0.01-0.1g/L, and the concentration of stabilizer is 0.01-0.026mmol/L.
The dosage of each component is not optional in the composite plating bath, but only each component is within the above range
Composite plating bath, composite plating bath are stablized, can normal plating；Otherwise composite plating bath can be made unstable and can not plating.
Preferably, the composite plating bath includes：The six hydration nickel sulfate of 27g/L, 24g/L a hydration sodium hypophosphite,
The lactic acid of 25g/L, the propionic acid of 2g/L, the thiocarbamide of 1mg/L, the graphene of the lauryl sodium sulfate of 1.2g/L and 0.04g/L.
The complexing agent dissociates acid ion in the plating solution, and acid ion is matched somebody with somebody as ligand and the nickel ion in plating solution
Position, prevents plating solution from separating out precipitation；And the ligand that lactic acid and propionic acid are formed with nickel ion, before deposition is reduced, Neng Goubao
Card nickel ion quickly shakes off the constraint of ligand, does not interfere with deposition velocity.Also, complexing agent can be adsorbed in matrix surface,
The catalytic activity of matrix is improved, increases deposition reaction speed.
As stabilizer, can play stably thiocarbamide effect with metal ion formation stable comple, suppress the spontaneous of plating solution
Decompose, and control the low sedimentation rate for being no more than 2mg/L, coating being effectively improved of thiourea concentration, and coating will not be produced
Toxic action.
In surfactant there is hydrophobic long alkyl chain to adsorb in graphene surface, pass through ionization stone
Black alkene surface is negatively charged, so as to produce the reunion that electrical charge rejection effect prevents graphene.Lauryl sodium sulfate is as surface
Activating agent, ionization, which produces dodecyl sulphate ion and sodium ion, wherein dodecyl sulphate ion, in the solution has long-chain
One of structure has hydrophobicity, can adsorb in graphene surface, so that graphene ribbon negative electricity, like charges are mutually exclusive,
So that graphene microchip is not easy to reunite.
Preferably, the preparation of the composite plating bath includes the following steps：By nickel salt solution, ortho phosphorous acid salting liquid and stabilization
Agent is sequentially added in the liquid containing complexing agent, is sufficiently stirred；Surfactant and graphene are added, ultrasound is fully dispersed, adjusts
The pH to 4-5 of plating solution is saved, obtains the composite plating bath.It is furthermore preferred that graphene and surfactant are premixed, frequency is used
Rate is that the ultrasound of 35-45kHz is disperseed.It is further preferred that supersonic frequency during ultrasonic disperse is 40kHz.
Preferably, described matrix is the metal with catalytic activity, preferably stainless steel.
Preferably, the useful load of the plating is 0.5-2dm2/L.It is furthermore preferred that the useful load of the plating is 1dm2/L。
By controlling matrix to need the area of plating and the ratio of the volume of composite plating bath, matrix surface can effectively ensure that
Uniformly plate graphene-phosphatization nickel composite deposite.
Preferably, the pretreatment of described matrix includes the following steps：Matrix is polished, at alkaline degreasing and acid-wash activation
Reason, washing obtain matrix.Matrix is obtained it is furthermore preferred that being washed using deionized water.
Preferably, the alkaline degreasing includes sodium carbonate, tricresyl phosphate in 50-70 DEG C of progress, the solution of the alkaline degreasing
Sodium and sodium hydroxide.It is furthermore preferred that the tertiary sodium phosphate of the sodium carbonate of the solution of the alkaline degreasing including 35g/L, 15g/L and
The sodium hydroxide of 7.5g/L.
Preferably, the acid-wash activation processing is carried out in 50-70 DEG C in diluted acid.It is furthermore preferred that the matter of the diluted acid
Amount fraction is 2%-6%.It is further preferred that the diluted acid includes dilute hydrochloric acid and dilute sulfuric acid.
By pretreatment, the corrosion layer and greasy dirt of matrix surface are eliminated, and makes matrix surface that there is catalytic activity, favorably
In the attachment and growth of coating.
Present invention also offers the stone that a kind of preparation method by the graphene-phosphatization nickel composite deposite is prepared
Black alkene-phosphatization nickel composite deposite, the phosphorus content 7-9wt% of the composite deposite, graphene content 5-7wt%.The Composite Coatings
After heat treatment, its Vickers hardness is about 1184 to layer, and Young's modulus is about 250GPa.
Compared with prior art, beneficial effects of the present invention are：
(1) graphene-phosphatization nickel composite deposite of the invention disperses graphene uniform by ultrasonic wave added, and is changing
During learning plating, ultrasonic cavitation improves the deposition velocity of coating, effectively improves the pin hole and bubble of coating surface
Defect, makes the structure of composite deposite that is prepared finer and close；
(2) preparation method of the present invention, it is ultrasonic while ensureing that graphene is fully dispersed during plating,
The micro-bubble in plating solution can be made to be vibrated under the action of ultrasonic field, and grow focused energy, bubble collapses when reaching threshold value
Burst and release energy, produce localized hyperthermia high pressure, promote the uniform mixing between each reactant in composite plating bath, accelerate reactant and
The diffusion of product, promotes the formation of solid cenotype, so as to improve the deposition velocity of composite deposite；
(3) the composite deposite phosphorus content 7-9wt% that the present invention is prepared, graphene content 5-7wt%, the Composite Coatings
After layer heat treatment, its Vickers hardness is about 1184, and Young's modulus is about 250GPa.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is the schematic flow diagram of the preparation method of graphene of the embodiment of the present invention-phosphatization nickel composite deposite；
The SEM photograph for graphene-phosphatization nickel composite deposite that Fig. 2 is prepared for institute's embodiment of the present invention；
Fig. 3 is the EDS energy spectrum diagrams for graphene-phosphatization nickel composite deposite that the embodiment of the present invention is prepared；
Fig. 4 is the surface topography for the phosphatization nickel coating that phosphatization nickel plating bath is prepared under no ultrasound condition；
Fig. 5 is the surface topography for the phosphatization nickel coating that phosphatization nickel plating bath is prepared in the case where there is ultrasound condition；
Fig. 6 is the thickness for the phosphatization nickel coating that phosphatization nickel plating bath is prepared under no ultrasound condition；
Fig. 7 is the thickness for the phosphatization nickel coating that phosphatization nickel plating bath is prepared in the case where there is ultrasound condition.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
Referring to Fig. 1, it is the exemplary flow of the preparation method of graphene of the embodiment of the present invention-phosphatization nickel composite deposite
Figure, the preparation method of graphene-phosphatization nickel composite deposite described in the present embodiment include the following steps：
(1) preparation of graphene：
Graphite flake is placed in the cathode of DC power supply, platinum electrode is placed in the anode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, change applied magnitude of voltage and voltage action time, peeled off, the stone that stripping is obtained
It is transferred to after black alkene vacuum filtration, deionized water cleaning in 1-methyl-2-pyrrolidinone, 48h is stood after ultrasonic disperse 30min.Take
Layer solution carries out vacuum filtration and deionized water cleaning, and the graphene microchip that collection obtains is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution, carries out surface modification to graphene microchip, enables graphene microchip dispersed.Institute in the present invention
The graphene of description is not the restriction to the number of plies, is not limited to the graphene of individual layer, and graphene of the invention includes 1-5 layers of list
The graphene microchip of layer graphene superposition.
Specifically, in electrolytic process, voltage 5min, Ran Houzai of the platinum electrode with graphite flake at a distance of 2cm, first application 1V
Apply the voltage 20min of 7.5V, the graphene size being prepared is 3-5 μm, and the number of plies is 1-5 layers.
(2) configuration of composite plating bath：
The component of the composite plating bath is：Nickel sulfate (the NiSO of 27g/L4·6H2O), the sodium hypophosphite of 24g/L
(NaH2PO2·H2O), the graphene of the lactic acid of 25g/L, the propionic acid of 2g/L, the thiocarbamide of 1mg/L, the SDS of 1.2g/L and 0.04g/L
Microplate.Wherein, the graphene microchip is the concentration being dispersed in solution.
Specifically, composite plating bath is prepared in accordance with the following steps：The mixed liquor of making lactic acid and propionic acid, in glass bar stirring bar
Under part, nickel sulfate solution is first slowly added into mixed solution, after addition, under glass bar stirring condition, more slowly
Addition ortho phosphorous acid sodium water solution, after addition, add thiourea solution, stir evenly；Then step (1) is added
In the graphene microchip that is modified of obtained lauryl sodium sulfate, 40kHz, which is ultrasonically treated, makes its fully dispersed, is eventually adding ammonium hydroxide
The pH to 4.6-4.8 of solution is adjusted, obtains the composite plating bath of mentioned component.
(3) substrate pretreated：
The basis material that the present embodiment uses is stainless steel.Configure alkaline degreasing solution and acid-wash activation processing solution, institute
The concentration for stating sodium carbonate in alkaline degreasing solution is 35g/L, the concentration of tertiary sodium phosphate is 15g/L, the concentration of sodium hydroxide is
7.5g/L；The acid-wash activation processing solution is the dilute hydrochloric acid that mass fraction is 4%, be by mass fraction be 35% concentrated hydrochloric acid
1 ﹕ 9 is formulated by volume with distilled water.
First stainless steel base is polished, then adds in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；Will
Matrix after oil removing is placed in acid-wash activation processing solution after deionized water is cleaned under 60 DEG C of water bath conditions, carries out pickling
Activation process；After the completion of activation, matrix is cleaned up, obtains surface cleaning and the matrix with catalytic activity.
Described matrix is not limited to this, can be metallic matrix and nonmetal basal body.The poor matrix of electric conductivity in this way, can
First to carry out sensitized treatment to matrix, activation process is then carried out by palladium metal again, palladium is attached to matrix surface, makes matrix
It is conductive.
(4) preparation of composite deposite：
Step (2) is prepared to obtained composite plating bath to be preheated, is preheated to 75 DEG C；The matrix that step (3) is pre-processed
Preheated, be preheated to 75 DEG C；Matrix is immersed in composite plating bath, composite plating bath and matrix are then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form the attachment of stabilization on matrix surface, is then turned on ultrasound under 75 DEG C of water bath conditions,
Supersonic frequency is 40kHz, and ultrasound is closed after 1min, ultrasound is then turned on after 10min, the condition being ultrasonically treated with this circular gap formula
Lower plating 2h, obtains the graphene-phosphatization nickel composite deposite.
Useful load during the plating is 1dm2/ L, i.e. matrix need the area of plating and the volume of composite plating bath
Than for 1dm2/L。
Embodiment 2
The preparation method of graphene-phosphatization nickel composite deposite described in the present embodiment includes the following steps：
(1) preparation of graphene：
Graphite flake is placed in the cathode of DC power supply, platinum electrode is placed in the anode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, change applied magnitude of voltage and voltage action time, peeled off, the stone that stripping is obtained
It is transferred to after black alkene vacuum filtration, deionized water cleaning in 1-methyl-2-pyrrolidinone, 48h is stood after ultrasonic disperse 30min.Take
Layer solution carries out vacuum filtration and deionized water cleaning, and the graphene microchip that collection obtains is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution, carries out surface modification to graphene microchip, enables graphene microchip dispersed.
Specifically, in electrolytic process, voltage 5min, Ran Houzai of the platinum electrode with graphite flake at a distance of 2cm, first application 1V
Apply the voltage 20min of 7.5V, the graphene size being prepared is 3-5 μm, and the number of plies is 1-5 layers.
(2) configuration of composite plating bath：
The component of the composite plating bath is：Nickel chloride (the NiCl of 12g/L2·6H2O), the sodium hypophosphite of 10.6g/L
(NaH2PO2·H2O), the graphite of the lactic acid of 9g/L, the propionic acid of 2g/L, the thiocarbamide of 0.76mg/L, the SDS of 0.5g/L and 0.01g/L
Alkene microplate.Wherein, the graphene microchip is the concentration being dispersed in solution.
Specifically, composite plating bath is prepared in accordance with the following steps：The mixed liquor of making lactic acid and propionic acid, in glass bar stirring bar
Under part, nickel sulfate solution is first slowly added into mixed solution, after addition, under glass bar stirring condition, more slowly
Addition ortho phosphorous acid sodium water solution, after addition, add thiourea solution, stir evenly；Then step (1) is added
In the graphene microchip that is modified of obtained lauryl sodium sulfate, supersound process makes its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH of solution to 4.4-4.6, obtains the composite plating bath of mentioned component.
(3) substrate pretreated：
The basis material that the present embodiment uses is stainless steel.Configure alkaline degreasing solution and acid-wash activation processing solution, institute
The concentration for stating sodium carbonate in alkaline degreasing solution is 35g/L, the concentration of tertiary sodium phosphate is 15g/L, the concentration of sodium hydroxide is
7.5g/L；The acid-wash activation processing solution is the dilute hydrochloric acid that mass fraction is 6%.
First stainless steel base is polished, then adds in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；Will
Matrix after oil removing is placed in acid-wash activation processing solution after deionized water is cleaned under 60 DEG C of water bath conditions, carries out pickling
Activation process；After the completion of activation, matrix is cleaned up, obtains surface cleaning and the matrix with catalytic activity.
(4) preparation of composite deposite：
Step (2) is prepared to obtained composite plating bath to be preheated, is preheated to 80 DEG C；The matrix that step (3) is pre-processed
Preheated, be preheated to 80 DEG C；Matrix is immersed in composite plating bath, composite plating bath and matrix are then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form the attachment of stabilization on matrix surface, is then turned on ultrasound under 80 DEG C of water bath conditions,
Ultrasound is closed after 0.5min, ultrasound is then turned on after 5min, plating 2h under conditions of being ultrasonically treated with this circular gap formula, obtains institute
State graphene-phosphatization nickel composite deposite.
Useful load during the plating is 0.5dm2/ L, i.e. matrix need the area of plating and the volume of composite plating bath
Ratio be 0.5dm2/L。
Embodiment 3
The preparation method of graphene-phosphatization nickel composite deposite described in the present embodiment includes the following steps：
(1) preparation of graphene：
Graphite flake is placed in the cathode of DC power supply, platinum electrode is placed in the anode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, change applied magnitude of voltage and voltage action time, peeled off, the stone that stripping is obtained
It is transferred to after black alkene vacuum filtration, deionized water cleaning in 1-methyl-2-pyrrolidinone, 48h is stood after ultrasonic disperse 30min.Take
Layer solution carries out vacuum filtration and deionized water cleaning, and the graphene microchip that collection obtains is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution, carries out surface modification to graphene microchip, enables graphene microchip dispersed.
Specifically, in electrolytic process, voltage 5min, Ran Houzai of the platinum electrode with graphite flake at a distance of 2cm, first application 1V
Apply the voltage 20min of 7.5V, the graphene size being prepared is 3-5 μm, and the number of plies is 1-5 layers.
(2) configuration of composite plating bath：
The component of the composite plating bath is：Nickel sulfate (the NiSO of 39g/L4·6H2O), the sodium hypophosphite of 32g/L
(NaH2PO2·H2O), the graphene of the lactic acid of 36g/L, the propionic acid of 7g/L, the thiocarbamide of 2mg/L, the SDS of 2.8g/L and 0.1g/L
Microplate.Wherein, the graphene microchip is the concentration being dispersed in solution.
Specifically, composite plating bath is prepared in accordance with the following steps：The mixed liquor of making lactic acid and propionic acid, in glass bar stirring bar
Under part, nickel sulfate solution is first slowly added into mixed solution, after addition, under glass bar stirring condition, more slowly
Addition ortho phosphorous acid sodium water solution, after addition, add thiourea solution, stir evenly；Then step (1) is added
In the graphene microchip that is modified of obtained lauryl sodium sulfate, supersound process makes its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH of solution to 4.6-4.8, obtains the composite plating bath of mentioned component.
(3) substrate pretreated：
The basis material that the present embodiment uses is stainless steel.Configure alkaline degreasing solution and acid-wash activation processing solution, institute
The concentration for stating sodium carbonate in alkaline degreasing solution is 35g/L, the concentration of tertiary sodium phosphate is 15g/L, the concentration of sodium hydroxide is
7.5g/L；The acid-wash activation processing solution is the dilute hydrochloric acid that mass fraction is 2%.
First stainless steel base is polished, then adds in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；Will
Matrix after oil removing is placed in acid-wash activation processing solution after deionized water is cleaned under 60 DEG C of water bath conditions, carries out pickling
Activation process；After the completion of activation, matrix is cleaned up, obtains surface cleaning and the matrix with catalytic activity.
(4) preparation of composite deposite：
Step (2) is prepared to obtained composite plating bath to be preheated, is preheated to 70 DEG C；The matrix that step (3) is pre-processed
Preheated, be preheated to 70 DEG C；Matrix is immersed in composite plating bath, composite plating bath and matrix are then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form the attachment of stabilization on matrix surface, is then turned on ultrasound under 70 DEG C of water bath conditions,
Ultrasound is closed after 1min, ultrasound is then turned on after 10min, plating 1h under conditions of being ultrasonically treated with this circular gap formula, obtains institute
State graphene-phosphatization nickel composite deposite.
Useful load during the plating is 2dm2/ L, i.e. matrix need the area of plating and the volume of composite plating bath
Than for 2dm2/L。
Embodiment 4
The preparation method of graphene-phosphatization nickel composite deposite described in the present embodiment includes the following steps：
(1) preparation of graphene：
Graphite flake is placed in the cathode of DC power supply, platinum electrode is placed in the anode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, change applied magnitude of voltage and voltage action time, peeled off, the stone that stripping is obtained
It is transferred to after black alkene vacuum filtration, deionized water cleaning in 1-methyl-2-pyrrolidinone, 48h is stood after ultrasonic disperse 30min.Take
Layer solution carries out vacuum filtration and deionized water cleaning, and the graphene microchip that collection obtains is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution, carries out surface modification to graphene microchip, enables graphene microchip dispersed.
Specifically, in electrolytic process, voltage 5min, Ran Houzai of the platinum electrode with graphite flake at a distance of 2cm, first application 1V
Apply the voltage 20min of 7.5V, the graphene size being prepared is 3-5 μm, and the number of plies is 1-5 layers.
(2) configuration of composite plating bath：
The component of the composite plating bath is：Nickel sulfate (the NiSO of 26g/L4·6H2O), the sodium hypophosphite of 21g/L
(NaH2PO2·H2O), the stone of the lactic acid of 18g/L, the propionic acid of 3.7g/L, the thiocarbamide of 1.5mg/L, the SDS of 1.1g/L and 0.03g/L
Black alkene microplate.Wherein, the graphene microchip is the concentration being dispersed in solution.
Specifically, composite plating bath is prepared in accordance with the following steps：The mixed liquor of making lactic acid and propionic acid, in glass bar stirring bar
Under part, nickel sulfate solution is first slowly added into mixed solution, after addition, under glass bar stirring condition, more slowly
Addition ortho phosphorous acid sodium water solution, after addition, add thiourea solution, stir evenly；Then step (1) is added
In the graphene microchip that is modified of obtained lauryl sodium sulfate, supersound process makes its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH of solution to 4.6-4.8, obtains the composite plating bath of mentioned component.
(3) substrate pretreated：
The basis material that the present embodiment uses is stainless steel.Configure alkaline degreasing solution and acid-wash activation processing solution, institute
The concentration for stating sodium carbonate in alkaline degreasing solution is 35g/L, the concentration of tertiary sodium phosphate is 15g/L, the concentration of sodium hydroxide is
7.5g/L；The acid-wash activation processing solution is the dilute hydrochloric acid that mass fraction is 2%.
First stainless steel base is polished, then adds in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；Will
Matrix after oil removing is placed in acid-wash activation processing solution after deionized water is cleaned under 60 DEG C of water bath conditions, carries out pickling
Activation process；After the completion of activation, matrix is cleaned up, obtains surface cleaning and the matrix with catalytic activity.
(4) preparation of composite deposite：
Step (2) is prepared to obtained composite plating bath to be preheated, is preheated to 90 DEG C；The matrix that step (3) is pre-processed
Preheated, be preheated to 90 DEG C；Matrix is immersed in composite plating bath, composite plating bath and matrix are then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form the attachment of stabilization on matrix surface, is then turned on ultrasound under 90 DEG C of water bath conditions,
Ultrasound is closed after 3min, ultrasound is then turned on after 15min, plating 3h under conditions of being ultrasonically treated with this circular gap formula, obtains institute
State graphene-phosphatization nickel composite deposite.
Useful load during the plating is 1dm2/ L, i.e. matrix need the area of plating and the volume of composite plating bath
Than for 1dm2/L。
Embodiment 5
The preparation method of graphene-phosphatization nickel composite deposite described in the present embodiment includes the following steps：
(1) preparation of graphene：
Graphite flake is placed in the cathode of DC power supply, platinum electrode is placed in the anode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, change applied magnitude of voltage and voltage action time, peeled off, the stone that stripping is obtained
It is transferred to after black alkene vacuum filtration, deionized water cleaning in 1-methyl-2-pyrrolidinone, 48h is stood after ultrasonic disperse 30min.Take
Layer solution carries out vacuum filtration and deionized water cleaning, and the graphene microchip that collection obtains is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution, carries out surface modification to graphene microchip, enables graphene microchip dispersed.
Specifically, in electrolytic process, voltage 5min, Ran Houzai of the platinum electrode with graphite flake at a distance of 2cm, first application 1V
Apply the voltage 20min of 7.5V, the graphene size being prepared is 3-5 μm, and the number of plies is 1-5 layers.
(2) configuration of composite plating bath：
The component of the composite plating bath is：Nickel sulfate (the NiSO of 30g/L4·6H2O), the sodium hypophosphite of 25g/L
(NaH2PO2·H2O), the graphite of the lactic acid of 28g/L, the propionic acid of 4g/L, the thiocarbamide of 1.5mg/L, the SDS of 1.7g/L and 0.06g/L
Alkene microplate.Wherein, the graphene microchip is the concentration being dispersed in solution.
Specifically, composite plating bath is prepared in accordance with the following steps：The mixed liquor of making lactic acid and propionic acid, in glass bar stirring bar
Under part, nickel sulfate solution is first slowly added into mixed solution, after addition, under glass bar stirring condition, more slowly
Addition ortho phosphorous acid sodium water solution, after addition, add thiourea solution, stir evenly；Then step (1) is added
In the graphene microchip that is modified of obtained lauryl sodium sulfate, supersound process makes its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH of solution to 4.6-4.8, obtains the composite plating bath of mentioned component.
(3) substrate pretreated：
The basis material that the present embodiment uses is stainless steel.Configure alkaline degreasing solution and acid-wash activation processing solution, institute
The concentration for stating sodium carbonate in alkaline degreasing solution is 35g/L, the concentration of tertiary sodium phosphate is 15g/L, the concentration of sodium hydroxide is
7.5g/L；The acid-wash activation processing solution is the dilute hydrochloric acid that mass fraction is 2%.
First stainless steel base is polished, then adds in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；Will
Matrix after oil removing is placed in acid-wash activation processing solution after deionized water is cleaned under 60 DEG C of water bath conditions, carries out pickling
Activation process；After the completion of activation, matrix is cleaned up, obtains surface cleaning and the matrix with catalytic activity.
(4) preparation of composite deposite：
Step (2) is prepared to obtained composite plating bath to be preheated, is preheated to 70 DEG C；The matrix that step (3) is pre-processed
Preheated, be preheated to 70 DEG C；Matrix is immersed in composite plating bath, composite plating bath and matrix are then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form the attachment of stabilization on matrix surface, is then turned on ultrasound under 70 DEG C of water bath conditions,
Ultrasound is closed after 3min, ultrasound is then turned on after 10min, plating 5h under conditions of being ultrasonically treated with this circular gap formula, obtains institute
State graphene-phosphatization nickel composite deposite.
Useful load during the plating is 1dm2/ L, i.e. matrix need the area of plating and the volume of composite plating bath
Than for 1dm2/L。
Embodiment 6
The preparation method of graphene-phosphatization nickel composite deposite described in the present embodiment includes the following steps：
(1) preparation of graphene：
Graphite flake is placed in the cathode of DC power supply, platinum electrode is placed in the anode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, change applied magnitude of voltage and voltage action time, peeled off, the stone that stripping is obtained
It is transferred to after black alkene vacuum filtration, deionized water cleaning in 1-methyl-2-pyrrolidinone, 48h is stood after ultrasonic disperse 30min.Take
Layer solution carries out vacuum filtration and deionized water cleaning, and the graphene microchip that collection obtains is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution, carries out surface modification to graphene microchip, enables graphene microchip dispersed.
Specifically, in electrolytic process, voltage 5min, Ran Houzai of the platinum electrode with graphite flake at a distance of 2cm, first application 1V
Apply the voltage 20min of 7.5V, the graphene size being prepared is 3-5 μm, and the number of plies is 1-5 layers.
(2) configuration of composite plating bath：
The component of the composite plating bath is：Nickel sulfate (the NiSO of 27g/L4·6H2O), the sodium hypophosphite of 24g/L
(NaH2PO2·H2O), the graphene of the lactic acid of 25g/L, the propionic acid of 2g/L, the thiocarbamide of 1mg/L, the SDS of 1.2g/L and 0.04g/L
Microplate.Wherein, the graphene microchip is the concentration being dispersed in solution.
Specifically, composite plating bath is prepared in accordance with the following steps：The mixed liquor of making lactic acid and propionic acid, in glass bar stirring bar
Under part, nickel sulfate solution is first slowly added into mixed solution, after addition, under glass bar stirring condition, more slowly
Addition ortho phosphorous acid sodium water solution, after addition, be slow added into thiourea solution, stir evenly；Then step is added
Suddenly the graphene microchip that obtained lauryl sodium sulfate is modified in (1), supersound process make its fully dispersed, are eventually adding ammonium hydroxide
The pH to 4.6-4.8 of solution is adjusted, obtains the composite plating bath of mentioned component.
(3) substrate pretreated：
The basis material that the present embodiment uses is stainless steel.Configure alkaline degreasing solution and acid-wash activation processing solution, institute
The concentration for stating sodium carbonate in alkaline degreasing solution is 35g/L, the concentration of tertiary sodium phosphate is 15g/L, the concentration of sodium hydroxide is
7.5g/L；The acid-wash activation processing solution is the dilute hydrochloric acid that mass fraction is 4%, be by mass fraction be 35% concentrated hydrochloric acid
1 ﹕ 9 is formulated by volume with distilled water.
First stainless steel base is polished, then adds in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；Will
Matrix after oil removing is placed in acid-wash activation processing solution after deionized water is cleaned under 60 DEG C of water bath conditions, carries out pickling
Activation process；After the completion of activation, matrix is cleaned up, obtains surface cleaning and the matrix with catalytic activity.
(4) preparation of composite deposite：
Step (2) is prepared to obtained composite plating bath to be preheated, is preheated to 75 DEG C；The matrix that step (3) is pre-processed
Preheated, be preheated to 75 DEG C；Matrix is immersed in composite plating bath, composite plating bath and matrix are then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form the attachment of stabilization on matrix surface, is then turned on ultrasound under 75 DEG C of water bath conditions,
Continuous ultrasound handles plating 2h, obtains the graphene-phosphatization nickel composite deposite.
Useful load during the plating is 1dm2/ L, i.e. matrix need the area of plating and the volume of composite plating bath
Than for 1dm2/L。
Experimental example 1
Referring to Fig. 2, it is that graphene-nickel phosphide that the preparation method described in the embodiment of the present invention 1 is prepared is multiple
The SEM photograph of coating is closed, as can be seen from the figure graphene-phosphatization nickel composite deposite surface is evenly distributed, compact structure, needleless
Hole defect.
Fig. 3 is the EDS for graphene-phosphatization nickel composite deposite that the preparation method described in the embodiment of the present invention 1 is prepared
Energy spectrum diagram.The composite deposite phosphorus content 7-9wt%, graphene content 5-7wt%.
The composite deposite is heat-treated, under nitrogen protection, is kept the temperature in 400 DEG C after 2h after furnace cooling, to it
Vickers hardness and Young's modulus are detected, its Vickers hardness is 1184, Young's modulus 250GPa.
Experimental example 2
For comparative illustration, by composite plating bath plating under no ultrasound condition, due to the presence of graphene in composite plating bath,
Graphene is reunited, and causes coating to prepare failure.
It is super using phosphatization nickel plating bath whether there is in order to further illustrate the influence being ultrasonically treated to the surface property of coating
The contrast experiment of sonication.The phosphatization nickel plating bath includes the nickel sulfate (NiSO of 27g/L4·6H2O), the ortho phosphorous acid of 24g/L
Sodium (NaH2PO2·H2O), the lactic acid of 25g/L, the propionic acid of 2g/L, the thiocarbamide of 1mg/L, the difference with the composite plating bath of embodiment 1
Essentially consist in and do not add graphene and surfactant.
Fig. 4 and Fig. 5 is the table for the phosphatization nickel coating that above-mentioned phosphatization nickel plating bath is prepared under no ultrasound condition respectively
Face pattern and the surface topography for having the phosphatization nickel coating being prepared under ultrasound condition.Plating method and implementation without ultrasound condition
Example 1 is similar, differs only in without being ultrasonically treated, has the plating method of ultrasound condition same as Example 1.
From Fig. 4 and Fig. 5 as can be seen that by after introducing and being ultrasonically treated, the quilt the defects of pinprick and stomata of coating surface
Substantially eliminate, be effectively improved surface property, improve uniformity, the compactness of coating.Due to the plating of the composite deposite of the present invention
During mainly phosphorus and nickel deposition, graphene the deposition of the two during plating is influenced it is little, by being plated to nickel phosphide
The presence or absence of layer is ultrasonically treated contrast, can learn the supersound process of the present invention and greatly improve the surface for the coating being prepared
Performance, compact structure, pin-free and air blister defect.
Experimental example 3
In order to further illustrate the influence being ultrasonically treated to thickness of coating and sedimentation rate, had using phosphatization nickel plating bath
Contrast experiment without supersound process.The phosphatization nickel plating bath includes the nickel sulfate (NiSO of 27g/L4·6H2O), time Asia of 24g/L
Sodium phosphate (NaH2PO2·H2O), the lactic acid of 25g/L, the propionic acid of 2g/L, the thiocarbamide of 1mg/L, with the composite plating bath of embodiment 1
Difference, which essentially consists in, does not add graphene and surfactant.
Fig. 6 and Fig. 7 is the thickness for the phosphatization nickel coating that above-mentioned phosphatization nickel plating bath is prepared under no ultrasound condition respectively
Spend and have the thickness for the phosphatization nickel coating being prepared under ultrasound condition.Plating method without ultrasound condition is similar to Example 1,
Differ only in without being ultrasonically treated, have the plating method of ultrasound condition same as Example 1.
It can be seen from figures 6 and 7 that after by introducing supersound process, the deposition velocity of coating is greatly improved.
Although being illustrated and the invention has been described with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. the preparation method of graphene-phosphatization nickel composite deposite, it is characterised in that include the following steps：
Graphene ultrasonic disperse is obtained into composite plating bath in phosphatization nickel plating bath, then the matrix of pretreatment is placed in composite plating bath
Carry out ultrasonic plating.
2. the preparation method of graphene according to claim 1-phosphatization nickel composite deposite, it is characterised in that between circulation
Have a rest plating under ultrasound condition；
Preferably, the circular gap ultrasound condition is single ultrasound 0.5-3min, interval 5-15min；It is it is furthermore preferred that described
Plating time is 0.5-3h.
3. the preparation method of graphene according to claim 1 or 2-phosphatization nickel composite deposite, it is characterised in that during plating
Ultrasonic frequency be 35-45kHz；
Preferably, ultrasonic frequency during plating is 40kHz.
4. the preparation method of graphene according to claim 1-phosphatization nickel composite deposite, it is characterised in that at 70-90 DEG C
Under the conditions of carry out plating；
Preferably, composite plating bath and matrix are preheated before plating, is preheated to 70-90 DEG C.
5. the preparation method of graphene according to claim 1-phosphatization nickel composite deposite, it is characterised in that described compound
Plating solution includes nickel salt, hypophosphite, complexing agent, surfactant and graphene；Preferably, also wrapped in the composite plating bath
Include stabilizer.
6. the preparation method of graphene according to claim 5-phosphatization nickel composite deposite, it is characterised in that described compound
The concentration of nickel salt is 0.05-0.15mol/L in plating solution, and the concentration of hypophosphite is 0.1-0.3mol/L, the concentration of complexing agent
For 0.1-0.5mol/L, the concentration of surfactant is 0.001-0.01mol/L, and the concentration of graphene is 0.01-0.1g/L, surely
The concentration for determining agent is 0.01-0.026mmol/L.
7. the preparation method of graphene-phosphatization nickel composite deposite according to claim 5 or 6, it is characterised in that described multiple
The preparation for closing plating solution includes the following steps：Nickel salt solution, ortho phosphorous acid salting liquid and stabilizer are sequentially added containing complexing agent
In liquid, it is sufficiently stirred；Surfactant and graphene are added, ultrasound is fully dispersed, adjusts the pH to 4-5 of plating solution, obtains
The composite plating bath；
Preferably, graphene and surfactant are premixed, ultrasonic disperse.
8. the preparation method of graphene according to claim 1-phosphatization nickel composite deposite, it is characterised in that described matrix
For the metal with catalytic activity, preferably stainless steel；
Preferably, the useful load of the plating is 0.5-2dm2/L；
It is furthermore preferred that the useful load of the plating is 1dm2/L。
9. the preparation method of graphene according to claim 1-phosphatization nickel composite deposite, it is characterised in that described matrix
Pretreatment include the following steps：Matrix is polished, the processing of alkaline degreasing and acid-wash activation, washing obtains matrix.
10. the graphite that the preparation method of claim 1-9 any one of them graphene-phosphatization nickel composite deposite is prepared
Alkene-phosphatization nickel composite deposite.
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