CN107916415B - Graphene-phosphatization nickel composite deposite preparation method and the coating being prepared - Google Patents
Graphene-phosphatization nickel composite deposite preparation method and the coating being prepared Download PDFInfo
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- CN107916415B CN107916415B CN201711167768.8A CN201711167768A CN107916415B CN 107916415 B CN107916415 B CN 107916415B CN 201711167768 A CN201711167768 A CN 201711167768A CN 107916415 B CN107916415 B CN 107916415B
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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 fields, specifically, the coating for being related to a kind of preparation method of graphene-phosphatization nickel composite deposite and being prepared, the graphene-phosphatization nickel composite deposite preparation method, include the following steps: to obtain graphene ultrasonic disperse into composite plating bath in phosphatization nickel plating bath, then pretreated matrix is placed in composite plating bath and carries out ultrasonic plating.Present invention introduces ultrasound and surfactants can make graphene fully dispersed during preparing composite plating bath and plating, effectively prevent 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, generate localized hyperthermia's high pressure, promote the uniform mixing in composite plating bath between each reactant, accelerate the diffusion of reactants and products, promotes solid New phase formation, improve the deposition velocity of composite deposite.
Description
Technical field
The present invention relates to composite deposite technical fields, in particular to a kind of graphene-phosphatization nickel composite deposite system
Preparation Method and the coating being prepared.
Background technique
Chemical plating nickel phosphide (Ni-P) coating is due to having 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 added to the comprehensive performance for being conducive to improve composite deposite in nickel phosphide (Ni-P) coating as reinforced phase.
In existing graphene-nickel phosphide (G-Ni-P) composite deposite preparation method, the coating of chemical plating method preparation
Since surface quality with higher and good binding force obtain the favor of researcher.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 passes through addition alcohol family macromolecule surfactant and using by way of magnetic agitation, makes graphene
It is evenly dispersed in the plating solution.However during magnetic agitation, graphene is easily adhered to for its surface of spontaneous reduction energy
In magnetic stir bar.Also, during chemical plating, continual magnetic agitation also will 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 dispersing in the solution, make graphene oxide
Surface is negatively charged, and generating electrostatic repulsion makes its stable dispersion in the solution.Therefore researcher first passes through chemical plating
It obtains graphene oxide-nickel phosphide (GO-Ni-P), then graphene oxide is reduced to by graphene by sodium borohydride reduction agent,
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, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of graphene-phosphatization nickel composite deposite, and described answers
The preparation method for closing coating disperses graphene uniform by ultrasonic wave added, and during chemical plating, and 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 to provide the preparation of graphene described in one kind-phosphatization nickel composite deposite preparation method
Obtained composite deposite, the composite deposite surface are evenly distributed, and coating structure is fine and close.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
Graphene-phosphatization nickel composite deposite preparation method, includes the following steps:
Graphene ultrasonic disperse is obtained into composite plating bath in phosphatization nickel plating bath, then pretreated matrix is placed in Composite Coatings
Ultrasonic plating is carried out in liquid.
Graphene of the invention-phosphatization nickel composite deposite preparation method is being matched by introducing ultrasound and surfactant
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 when threshold value, generates localized hyperthermia's high pressure, promotes the uniform mixing in composite plating bath between each reactant,
Graphene can be made fully dispersed, can effectively prevent the reunion of graphene, otherwise the reunion of graphene will affect coating comprehensive performance；
And during plating, while guaranteeing that graphene is fully dispersed, ultrasonic wave generates localized hyperthermia's high pressure in composite plating bath,
Promote the uniform mixing in composite plating bath between each reactant, accelerate the diffusion of reactants and products, promotes the shape of solid cenotype
At to improve the deposition velocity of composite deposite.In addition, the introducing of ultrasound effectively improves the pin hole and bubble of coating surface
Defect keeps coating structure finer and close.
Magnetic agitation in compared to the prior art improves the mode of graphene dispersion, 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 be disturbed.
Compared to the mode of redox graphene, preparation method of the invention is not necessarily to reduction process, reproducible, 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
Pretreated matrix 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 too long, and temperature is excessively high within the scope of above-mentioned plating time, when can be avoided plating causes to stone
Black alkene disperses detrimental effect.In this plating time, obtained coating with a thickness of 10-50 μm, advantageously ensure that coating
Uniformity, and meet subsequent mechanical processing requirement.
Also, continuous ultrasound will affect the nickel ion in solution in the adhesion on catalysis matrix surface, adheres to difficulty and increases,
Influence the deposition of phosphorus and nickel；Using the working method of interval ultrasound, it can guarantee that nickel ion is attached to matrix surface and is reduced.
Preferably, the frequency of ultrasound when plating is 35-45kHz.It is furthermore preferred that the frequency of the ultrasound when plating is
40kHz。
Preferably, the frequency of ultrasound when ultrasonic disperse is 35-45kHz.It is furthermore preferred that the ultrasound when ultrasonic disperse
Frequency be 40kHz.
Preferably, plating is carried out under the conditions of 70-90 DEG C.It is furthermore preferred that being carried out before plating to composite plating bath and matrix pre-
Heat is preheated to 70-90 DEG C.
Preferably, the graphene includes 1-5 layers of the number of plies of graphene microchip.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
Cathode, is dipped in the voltage value for changing application in electrolyte and voltage action time, and removing obtains the graphene.
It preferably, include nickel salt, hypophosphite, complexing agent, surfactant and graphene in the composite plating bath.More
It preferably, further include stabilizer in the composite plating bath.
Preferably, the nickel salt includes one or both of nickel sulfate and nickel chloride；The hypophosphite includes time
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 ingredient is not optional in the composite plating bath, and only each ingredient 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 include: the six hydration nickel sulfate of 27g/L, 24g/L one hydration sodium hypophosphite,
The lactic acid of 25g/L, the propionic acid of 2g/L, the thiocarbamide of 1mg/L, the lauryl sodium sulfate of 1.2g/L and the graphene of 0.04g/L.
The complexing agent dissociates acid ion in the plating solution, and acid ion is matched as ligand and the nickel ion in plating solution
Position prevents plating solution that precipitating is precipitated；And the ligand that lactic acid and propionic acid and nickel ion are formed, before being reduced deposition, Neng Goubao
Card nickel ion quickly shakes off the constraint of ligand, will not influence deposition velocity.Also, complexing agent can be adsorbed on matrix surface,
The catalytic activity of matrix is improved, deposition reaction speed is increased.
Thiocarbamide is as stabilizer, and can play stably effect with metal ion formation stable comple, inhibits the spontaneous of plating solution
It decomposes, and control thiourea concentration is low no more than 2mg/L, can effectively improve the deposition rate of coating, and will not generate to coating
Toxic action.
There is the absorption of hydrophobic long alkyl chain on the surface of graphene in surfactant, stone is made by ionization
Black alkene surface is negatively charged, to generate the reunion that electrical charge rejection effect prevents graphene.Lauryl sodium sulfate is as surface
Activating agent, ionization generates dodecyl sulphate ion and sodium ion in the solution, and wherein dodecyl sulphate ion has long-chain
One of structure has hydrophobicity, can adsorb on the surface of graphene, to make graphene ribbon negative electricity, like charges are mutually exclusive,
It is easy to reunite to make graphene microchip not allow.
Preferably, the preparation of the composite plating bath includes the following steps: nickel salt solution, ortho phosphorous acid salting liquid and stabilization
Agent sequentially adds in the liquid containing complexing agent, is sufficiently stirred；Surfactant and graphene are added, ultrasound is fully dispersed, adjusts
The pH to 4-5 for saving plating solution, 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 dispersed.It is further preferred that supersonic frequency when 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。
The ratio that the area of plating and the volume of composite plating bath are needed by controlling matrix, can effectively ensure that matrix surface
Uniformly plate graphene-phosphatization nickel composite deposite.
Preferably, the pretreatment of described matrix includes the following steps: matrix to be polished, at alkaline degreasing and acid-wash activation
Reason, washing obtain matrix.Matrix is obtained it is furthermore preferred that washing using deionized water.
Preferably, the alkaline degreasing is carried out in 50-70 DEG C, and the solution of the alkaline degreasing includes sodium carbonate, tricresyl phosphate
Sodium and sodium hydroxide.It is furthermore preferred that the solution of the alkaline degreasing include the sodium carbonate of 35g/L, 15g/L tertiary sodium phosphate and
The sodium hydroxide of 7.5g/L.
Preferably, the acid-wash activation processing carries out in diluted acid in 50-70 DEG C.It is furthermore preferred that the matter of the diluted acid
Amount score 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.
The present invention also provides a kind of stones being prepared by the graphene-phosphatization nickel composite deposite preparation method
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, Vickers hardness is about 1184 to layer, and Young's modulus is about 250GPa.
Compared with prior art, the invention has the benefit that
(1) graphene of the invention-phosphatization nickel composite deposite 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 keeps the structure for the composite deposite being prepared finer and close；
(2) preparation method of the present invention, it is ultrasonic while guaranteeing that graphene is fully dispersed during plating,
The micro-bubble in plating solution can be made to vibrate under the action of ultrasonic field, and grow focused energy, bubble collapses when reaching threshold value
Burst and release energy, generate localized hyperthermia's high pressure, promote the uniform mixing in composite plating bath between each reactant, accelerate reactant and
The diffusion of product promotes the formation of solid cenotype, 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, Vickers hardness is about 1184, and Young's modulus is about 250GPa.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the schematic flow diagram of graphene of the embodiment of the present invention-phosphatization nickel composite deposite preparation method；
Graphene-phosphatization nickel composite deposite SEM photograph that Fig. 2 is prepared for institute's embodiment of the present invention；
Fig. 3 is graphene-phosphatization nickel composite deposite EDS energy spectrum diagram 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.
Specific 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 carries out according to conventional conditions or manufacturer's recommended conditions.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 graphene of the embodiment of the present invention-phosphatization nickel composite deposite preparation method
Scheme, graphene-phosphatization nickel composite deposite preparation method described in the present embodiment includes the following steps:
(1) preparation of graphene:
Graphite flake is placed in the anode of DC power supply, platinum electrode is placed in the cathode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, changes applied voltage value and voltage action time, removed, the stone that removing is obtained
It is transferred in N-Methyl pyrrolidone after black alkene vacuum filtration, deionized water cleaning, stands 48h after ultrasonic disperse 30min.It takes
Layer solution carries out vacuum filtration and deionized water cleaning, will collect obtained graphene microchip and is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution carries out surface to graphene microchip and is modified, keeps graphene microchip evenly 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 single layer, and graphene of the invention includes 1-5 layers of list
The graphene microchip of layer graphene superposition.
Specifically, platinum electrode and graphite flake first apply the voltage 5min of 1V, then again at a distance of 2cm in electrolytic process
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 ingredient of the composite plating bath are as follows: the nickel sulfate (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, preparing composite plating bath 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 modified graphene microchip of lauryl sodium sulfate obtained, 40kHz ultrasonic treatment keeps its fully dispersed, is eventually adding ammonium hydroxide
The pH to 4.6-4.8 for adjusting solution, 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%, is the concentrated hydrochloric acid for being 35% by mass fraction
1 ﹕ 9 is formulated by volume with distilled water.
First stainless steel base is polished, is then added in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；It 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
It is activated；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, then it is activated again by palladium metal, palladium is made to be attached to matrix surface, make matrix
It is conductive.
(4) preparation of composite deposite:
Step (2) are prepared obtained composite plating bath to preheat, are preheated to 75 DEG C；By step (3) pretreated matrix
It is preheated, is preheated to 75 DEG C；It immerses the substrate in composite plating bath, composite plating bath and matrix is then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form stable attachment 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, is then turned on ultrasound 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
Graphene described in the present embodiment-phosphatization nickel composite deposite preparation method includes the following steps:
(1) preparation of graphene:
Graphite flake is placed in the anode of DC power supply, platinum electrode is placed in the cathode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, changes applied voltage value and voltage action time, removed, the stone that removing is obtained
It is transferred in N-Methyl pyrrolidone after black alkene vacuum filtration, deionized water cleaning, stands 48h after ultrasonic disperse 30min.It takes
Layer solution carries out vacuum filtration and deionized water cleaning, will collect obtained graphene microchip and is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution carries out surface to graphene microchip and is modified, keeps graphene microchip evenly dispersed.
Specifically, platinum electrode and graphite flake first apply the voltage 5min of 1V, then again at a distance of 2cm in electrolytic process
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 ingredient of the composite plating bath are as follows: the nickel chloride (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, preparing composite plating bath 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 modified graphene microchip of lauryl sodium sulfate obtained, ultrasonic treatment keeps its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH to 4.4-4.6 of solution, 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, is then added in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；It 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
It is activated；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) are prepared obtained composite plating bath to preheat, are preheated to 80 DEG C；By step (3) pretreated matrix
It is preheated, is preheated to 80 DEG C；It immerses the substrate in composite plating bath, composite plating bath and matrix is then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form stable attachment on matrix surface, is then turned on ultrasound under 80 DEG C of water bath conditions,
Ultrasound is closed after 0.5min, is then turned on ultrasound after 5min, with plating 2h under conditions of this circular gap formula ultrasonic treatment, 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
Graphene described in the present embodiment-phosphatization nickel composite deposite preparation method includes the following steps:
(1) preparation of graphene:
Graphite flake is placed in the anode of DC power supply, platinum electrode is placed in the cathode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, changes applied voltage value and voltage action time, removed, the stone that removing is obtained
It is transferred in N-Methyl pyrrolidone after black alkene vacuum filtration, deionized water cleaning, stands 48h after ultrasonic disperse 30min.It takes
Layer solution carries out vacuum filtration and deionized water cleaning, will collect obtained graphene microchip and is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution carries out surface to graphene microchip and is modified, keeps graphene microchip evenly dispersed.
Specifically, platinum electrode and graphite flake first apply the voltage 5min of 1V, then again at a distance of 2cm in electrolytic process
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 ingredient of the composite plating bath are as follows: the nickel sulfate (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, preparing composite plating bath 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 modified graphene microchip of lauryl sodium sulfate obtained, ultrasonic treatment keeps its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH to 4.6-4.8 of solution, 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, is then added in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；It 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
It is activated；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) are prepared obtained composite plating bath to preheat, are preheated to 70 DEG C；By step (3) pretreated matrix
It is preheated, is preheated to 70 DEG C；It immerses the substrate in composite plating bath, composite plating bath and matrix is then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form stable attachment on matrix surface, is then turned on ultrasound under 70 DEG C of water bath conditions,
Ultrasound is closed after 1min, is then turned on ultrasound after 10min, with plating 1h under conditions of this circular gap formula ultrasonic treatment, 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
Graphene described in the present embodiment-phosphatization nickel composite deposite preparation method includes the following steps:
(1) preparation of graphene:
Graphite flake is placed in the anode of DC power supply, platinum electrode is placed in the cathode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, changes applied voltage value and voltage action time, removed, the stone that removing is obtained
It is transferred in N-Methyl pyrrolidone after black alkene vacuum filtration, deionized water cleaning, stands 48h after ultrasonic disperse 30min.It takes
Layer solution carries out vacuum filtration and deionized water cleaning, will collect obtained graphene microchip and is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution carries out surface to graphene microchip and is modified, keeps graphene microchip evenly dispersed.
Specifically, platinum electrode and graphite flake first apply the voltage 5min of 1V, then again at a distance of 2cm in electrolytic process
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 ingredient of the composite plating bath are as follows: the nickel sulfate (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, preparing composite plating bath 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 modified graphene microchip of lauryl sodium sulfate obtained, ultrasonic treatment keeps its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH to 4.6-4.8 of solution, 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, is then added in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；It 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
It is activated；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) are prepared obtained composite plating bath to preheat, are preheated to 90 DEG C；By step (3) pretreated matrix
It is preheated, is preheated to 90 DEG C；It immerses the substrate in composite plating bath, composite plating bath and matrix is then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form stable attachment on matrix surface, is then turned on ultrasound under 90 DEG C of water bath conditions,
Ultrasound is closed after 3min, is then turned on ultrasound after 15min, with plating 3h under conditions of this circular gap formula ultrasonic treatment, 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
Graphene described in the present embodiment-phosphatization nickel composite deposite preparation method includes the following steps:
(1) preparation of graphene:
Graphite flake is placed in the anode of DC power supply, platinum electrode is placed in the cathode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, changes applied voltage value and voltage action time, removed, the stone that removing is obtained
It is transferred in N-Methyl pyrrolidone after black alkene vacuum filtration, deionized water cleaning, stands 48h after ultrasonic disperse 30min.It takes
Layer solution carries out vacuum filtration and deionized water cleaning, will collect obtained graphene microchip and is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution carries out surface to graphene microchip and is modified, keeps graphene microchip evenly dispersed.
Specifically, platinum electrode and graphite flake first apply the voltage 5min of 1V, then again at a distance of 2cm in electrolytic process
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 ingredient of the composite plating bath are as follows: the nickel sulfate (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, preparing composite plating bath 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 modified graphene microchip of lauryl sodium sulfate obtained, ultrasonic treatment keeps its fully dispersed, is eventually adding ammonium hydroxide adjusting
The pH to 4.6-4.8 of solution, 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, is then added in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；It 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
It is activated；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) are prepared obtained composite plating bath to preheat, are preheated to 70 DEG C；By step (3) pretreated matrix
It is preheated, is preheated to 70 DEG C；It immerses the substrate in composite plating bath, composite plating bath and matrix is then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form stable attachment on matrix surface, is then turned on ultrasound under 70 DEG C of water bath conditions,
Ultrasound is closed after 3min, is then turned on ultrasound after 10min, with plating 5h under conditions of this circular gap formula ultrasonic treatment, 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
Graphene described in the present embodiment-phosphatization nickel composite deposite preparation method includes the following steps:
(1) preparation of graphene:
Graphite flake is placed in the anode of DC power supply, platinum electrode is placed in the cathode of DC power supply, is dipped in 0.5mol/L sulphur
In the electrolyte of sour aqueous ammonium, changes applied voltage value and voltage action time, removed, the stone that removing is obtained
It is transferred in N-Methyl pyrrolidone after black alkene vacuum filtration, deionized water cleaning, stands 48h after ultrasonic disperse 30min.It takes
Layer solution carries out vacuum filtration and deionized water cleaning, will collect obtained graphene microchip and is transferred to lauryl sodium sulfate water
Ultrasonic disperse 3h in solution carries out surface to graphene microchip and is modified, keeps graphene microchip evenly dispersed.
Specifically, platinum electrode and graphite flake first apply the voltage 5min of 1V, then again at a distance of 2cm in electrolytic process
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 ingredient of the composite plating bath are as follows: the nickel sulfate (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, preparing composite plating bath 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 modified graphene microchip of lauryl sodium sulfate obtained, ultrasonic treatment keep its fully dispersed, are eventually adding ammonium hydroxide in (1)
The pH to 4.6-4.8 for adjusting solution, 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%, is the concentrated hydrochloric acid for being 35% by mass fraction
1 ﹕ 9 is formulated by volume with distilled water.
First stainless steel base is polished, is then added in alkaline degreasing solution, oil removing is carried out under 60 DEG C of water bath conditions；It 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
It is activated；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) are prepared obtained composite plating bath to preheat, are preheated to 75 DEG C；By step (3) pretreated matrix
It is preheated, is preheated to 75 DEG C；It immerses the substrate in composite plating bath, composite plating bath and matrix is then placed in ultrasonic water bath pot
In, first preplating 20min, makes coating form stable attachment 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 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 graphene-phosphatization nickel composite deposite EDS that 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, after 400 DEG C of heat preservation 2h after furnace cooling, to it
Vickers hardness and Young's modulus are detected, Vickers hardness 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 coating preparation failure is caused.
Influence in order to further illustrate ultrasonic treatment to the surface property of coating, using the progress of phosphatization nickel plating bath, whether there is or not super
The comparative experiments 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 thiocarbamide of the lactic acid of 25g/L, the propionic acid of 2g/L, 1mg/L, the difference with the composite plating bath of embodiment 1
It essentially consists in and does 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, and difference is only that without ultrasonic treatment, has the plating method of ultrasound condition same as Example 1.
From in Fig. 4 and Fig. 5 as can be seen that after by introducing ultrasonic treatment, the quilt the defects of pinprick and stomata of coating surface
It substantially eliminates, is effectively improved surface property, improve uniformity, the compactness of coating.Due to the plating of composite deposite of the invention
It is in the process mainly the deposition of phosphorus and nickel, graphene influences less, by plating to nickel phosphide the deposition both during plating
The ultrasonic treatment comparison of the presence or absence of layer can learn that ultrasonic treatment of the invention greatly improves the surface for the coating being prepared
Performance, compact structure, pin-free and air blister defect.
Experimental example 3
Influence in order to further illustrate ultrasonic treatment to thickness of coating and deposition rate, is had using phosphatization nickel plating bath
Comparative experiments without ultrasonic treatment.The phosphatization nickel plating bath includes the nickel sulfate (NiSO of 27g/L4·6H2O), time Asia of 24g/L
Sodium phosphate (NaH2PO2·H2O), the thiocarbamide of the lactic acid of 25g/L, the propionic acid of 2g/L, 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,
Difference is only that without ultrasonic treatment, has the plating method of ultrasound condition same as Example 1.
It can be seen from figures 6 and 7 that greatly improving the deposition velocity of coating after by introducing ultrasonic treatment.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where 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 (12)
1. graphene-phosphatization nickel composite deposite preparation method, which comprises the steps of:
Graphene ultrasonic disperse is obtained into composite plating bath in phosphatization nickel plating bath, then pretreated matrix is placed in composite plating bath
The plating 0.5-3h under circular gap ultrasound condition；
The circular gap ultrasound condition is single ultrasound 0.5-3min, interval 5-15min；
When plating, the frequency of the ultrasound is 35-45kHz；
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 is 0.1-0.5mol/L, and the concentration of surfactant is 0.001-0.01mol/L, and the concentration of graphene is
0.01-0.1g/L, the concentration of stabilizer are 0.01-0.026mmol/L.
2. graphene according to claim 1-phosphatization nickel composite deposite preparation method, which is characterized in that when plating
The frequency of ultrasound is 40kHz.
3. graphene according to claim 1-phosphatization nickel composite deposite preparation method, which is characterized in that at 70-90 DEG C
Under the conditions of carry out plating.
4. graphene according to claim 1-phosphatization nickel composite deposite preparation method, which is characterized in that right before plating
Composite plating bath and matrix are preheated, and are preheated to 70-90 DEG C.
5. graphene according to claim 1-phosphatization nickel composite deposite preparation method, which is characterized in that described compound
The preparation of plating solution includes the following steps: nickel salt solution, ortho phosphorous acid salting liquid and stabilizer sequentially adding the liquid containing complexing agent
In body, it is sufficiently stirred；Surfactant and graphene are added, ultrasound is fully dispersed, adjusts the pH to 4-5 of plating solution, obtains institute
State composite plating bath.
6. graphene according to claim 5-phosphatization nickel composite deposite preparation method, which is characterized in that by graphene
It is premixed with surfactant, ultrasonic disperse.
7. graphene according to claim 1-phosphatization nickel composite deposite preparation method, which is characterized in that described matrix
For the metal with catalytic activity.
8. graphene according to claim 7-phosphatization nickel composite deposite preparation method, which is characterized in that described matrix
For stainless steel.
9. graphene according to claim 1-phosphatization nickel composite deposite preparation method, which is characterized in that the plating
Useful load be 0.5-2dm2/L。
10. graphene according to claim 9-phosphatization nickel composite deposite preparation method, which is characterized in that the plating
Useful load be 1dm2/L。
11. graphene according to claim 1-phosphatization nickel composite deposite preparation method, which is characterized in that described matrix
Pretreatment include the following steps: by matrix polish, alkaline degreasing and acid-wash activation processing, washing obtain matrix.
12. the graphite that the described in any item graphenes of claim 1-11-phosphatization nickel composite deposite preparation method is prepared
Alkene-phosphatization nickel composite deposite.
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