CN109371440A - TC4The method of titanium alloy surface plating medium Copper-Graphite Composite - Google Patents
TC4The method of titanium alloy surface plating medium Copper-Graphite Composite Download PDFInfo
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- CN109371440A CN109371440A CN201810751633.4A CN201810751633A CN109371440A CN 109371440 A CN109371440 A CN 109371440A CN 201810751633 A CN201810751633 A CN 201810751633A CN 109371440 A CN109371440 A CN 109371440A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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Abstract
The invention belongs to titanium alloy surface electroplating technologies, and in particular to a kind of TC4The method of titanium alloy surface plating medium Copper-Graphite Composite.For the problem that the existing cladding wearability energy formed in titanium alloy surface copper facing is poor, the present invention provides a kind of TC4The method of titanium alloy surface plating medium Copper-Graphite Composite, comprising the following steps: nitric acid roughening is added in a, by graphite powder calcination；Copper-bath and sulfuric acid solution are mixed to form electroplate liquid, graphite is added in electroplate liquid；B, to TC4Titanium alloy surface oil removal treatment, then carry out acid attack activation；C, electroplate liquid is added in electrolytic cell, the titanium alloy that step b is obtained is assembled into cathode with metal molybdenum filament, copper sheet is anode, stirs electroplate liquid, is electrolysed 10~60min at normal temperature, is then electroplated to obtain medium Copper-Graphite Composite in titanium alloy surface.Electro-plating method of the present invention is easy to operate, can be electroplated and obtain copper-graphite composite deposite, and the cladding wearability is more preferable, is worth higher.
Description
Technical field
The invention belongs to titanium alloy surface electroplating technologies, and in particular to a kind of TC4Copper-graphite is electroplated in titanium alloy surface
The method of composite material.
Background technique
Composite deposite refers to obtain the material of certain property, and it is insoluble that certain is purposefully added in general plating solution
The particle of property, is allowed to be co-deposited to coating prepared by substrate material surface with plating solution intermediate ion after being uniformly dispersed.With science
Technology is constantly progressive, and the performance requirement of material is also continuously improved, and traditional metal surface coating is not able to satisfy work increasingly
Skill is to various requirements such as the wearability of material, surface hardness, corrosion resistance, electric conductivity and self-lubrication.Therefore, in order to
The quality of coating is improved, the research of composite deposite is more and more.
Such as: SiC is added into traditional nickel-plating liquid in anti-friction abrasion and abrasive wear performance in order to improve piece surface
Particle carries out electro-deposition, Ni-SiC composite deposite can be obtained, wear-resisting property is higher than common nickel coating by about 70%, is applicable to
The aluminum alloy part of automobile engine.
In order to improve the self-lubrication of material surface, polytetrafluoroethylene (PTFE) particle is distributed to using nickel sulfate as nickel salt, secondary phosphorus
To carry out Ni-P in the chemical nickel-plating solution of reducing agent Ni-P-PTFE composite deposite can be obtained, the Composite Coatings in sour sodium
Layer, which is suitably applied, should move the occasion that (or heat-resisting) seals again.
Titanium alloy is a kind of metal alloy for being widely used in aerospace, chemical industry and biologic medical field, hardness compared with
Low, antiwear and friction reduction property is poor.In order to improve its performance, copper facing generally is carried out on its surface.Copper has fusing point height, plasticity good
Feature is applied in titanium alloy surface, and reduction coefficient of friction can be reached, and reduces frictional force, is rubbed to metal material surface is improved
Wiping polishing machine has good effect, can be improved the wearability and resistance to bond of titanium alloy.Currently, being plated in titanium alloy surface
When copper, the methods of plating, chemical plating, anodic oxidation, differential arc oxidation are mostly used to improve and improve the combination of matrix and coat
Power and the corrosion resisting property on surface, chemical plating, anodic oxidation, the obtained oxidation film layer of differential arc oxidation are relatively thin, corrosion resistance and resistance to
Long property is poor.
Patent CN102286763A discloses a kind of TC4The process of titanium alloy surface electro-coppering, successively to sample or
Workpiece carries out alkali cleaning oil removing degreasing, washing, bite, washing, activation processing, washing, plating, cleaning, surface passivation, clear
It washes and dries, can be electroplated to obtain copper coating in titanium alloy surface, but the cladding wearability is also poor, need to be improved.
Summary of the invention
The technical problem to be solved in the present invention are as follows: the existing cladding wearability formed in titanium alloy surface copper facing can be poor
Problem.
The technical solution of present invention solution above-mentioned technical problem are as follows: a kind of TC is provided4It is multiple that copper-graphite is electroplated in titanium alloy surface
The method of condensation material.Method includes the following steps:
A, by graphite powder calcination, nitric acid roughening is added, cleans, drying for standby；Copper-bath is mixed with sulfuric acid solution
Electroplate liquid is formed, graphite is added in electroplate liquid, 180~200g/l of concentration of copper sulfate in electroplate liquid, sulfuric acid concentration 40 are made
~60g/l, graphite concentration are 20~40vol%；
B, to TC4Titanium alloy surface oil removal treatment, then acid attack activation is carried out, it cleans, drying for standby；
C, electroplate liquid is added in electrolytic cell, the titanium alloy that step b is obtained is assembled into cathode with metal molybdenum filament, copper sheet is
Anode stirs electroplate liquid, is electrolysed 10~60min at normal temperature, is then electroplated to obtain copper-graphite composite deposite in titanium alloy surface.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, and graphite powder described in step a is
5~10um of partial size, 2.0~2.4g/cm of density3Graphite powder.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, the temperature of calcination described in step a
Degree is 380~450 DEG C, and calcination time is 1~2h.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, the concentration of nitric acid described in step a
It is 30~35%, the weight ratio or volume ratio of graphite powder and nitric acid are 1 ︰ 3~4.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, and the roughening of nitric acid described in step a is
Refer to after nitric acid is added, boils 10~20min.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, oil removal treatment described in step b
Concrete operations are as follows: titanium alloy is cleaned using acetone or gasoline, places into 5~10min of immersion in 80~100 DEG C of NaOH.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, and acid attack described in step b is living
The specific steps of change are as follows: titanium alloy is kept the temperature into 2~10min in 50~80 DEG C of water, then be placed in acid attack liquid impregnate 3~
5min, place into HCl solution impregnate 2~5min to get.
Further, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, the acid attack liquid
For mass concentration be 20~40% HF and mass concentration be 45~65% HNO33~4 ︰ 1 are mixed to get molten by volume
Liquid.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, the speed of stirring described in step c
For 400~500rpm.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, copper sheet purity described in step c
>=99.9%.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, electric current when being electroplated described in step c
Density is 2.5~4.5A/dm2。
Preferably, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, electrolysis time described in step c
For 20~40min.
The present invention also provides a kind of TC prepared by the above method4Titanium alloy composite deposite.
The invention has the benefit that
The present invention provides one kind in TC4Titanium alloy surface be electroplated medium Copper-Graphite Composite method, this method by pair
Titanium alloy surface is handled, so that the binding force of titanium alloy and plating solution enhances, obtains uniform, cause in titanium electroplating surface for the first time
Close composite deposite overcomes and obtains the technological difficulties of uniform, fine and close composite deposite in titanium electroplating surface Composite Coatings.This hair
Bright simpler compared with traditional chemical-copper-plating process, more convenient operation is at low cost, high-efficient.It is multiple that the present invention also provides one kind
Coating is closed, the coating is uniformly, fine and close, wearability is more preferable, under the conditions of same process, reduces than existing copper coating abrasion loss
0.4mm3/ h has widened the application field of titanium alloy, has apparent economic benefit.
Specific embodiment
The present invention provides a kind of TC4The method of titanium alloy surface plating medium Copper-Graphite Composite, comprising the following steps:
A, by graphite powder calcination, nitric acid roughening is added, cleans, drying for standby；Copper-bath is mixed with sulfuric acid solution
Electroplate liquid is formed, graphite is added in electroplate liquid, 180~200g/l of concentration of copper sulfate in electroplate liquid, sulfuric acid concentration 40 are made
~60g/l, graphite concentration are 20~40vol%；
B, to TC4Titanium alloy surface oil removal treatment, then acid attack activation is carried out, it cleans, drying for standby；
C, electroplate liquid is added in electrolytic cell, the titanium alloy that step b is obtained is assembled into cathode with metal molybdenum filament, copper sheet is
Anode stirs electroplate liquid, is electrolysed 10~60min at normal temperature, is then electroplated to obtain copper-graphite composite deposite in titanium alloy surface.
Key point of the invention is: in TC4The composite material of copper-graphite is electroplated in titanium alloy surface, when compared to copper facing,
Obtained composite deposite wear-resisting property is more preferable.Graphite is a kind of powder of black gray expandable, has flat crystal structure, greasy property
Good but also there is good conductive, thermally conductive, wear-resisting, pressure-resistant, heatproof (temperature may be up to 450 DEG C) and chemical stability
The features such as can be used as lubricant, by graphite deposits into copper, improve the lubricity of composite deposite, and then improve wear-resisting property.
Graphite powder is added in the present invention in the plating solution, is electroplated by electric plating method in titanium alloy surface, is on the one hand utilized
On the other hand the electric conductivity of graphite is electroplated using copper-graphite, can obtain a kind of composite deposite, significantly increase plating
The wear-resisting property of layer.It is preferred that using 5~10um of partial size, density for 2.0~2.4g/cm3Graphite powder, graphite partial size should not mistake
Small, too small easy reunion is not easy to be electroplated；Partial size also should not be too large, and partial size titanium is easy to be deposited to bottom greatly, be unfavorable for electro-deposition.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, the temperature of calcination described in step a
Degree is 380~450 DEG C, and calcination time is 1~2h.Calcination is first carried out before graphite powder plating, graphite powder can be activated, it can be with
The ash content and impurity for removing graphite powder surface make it combine power enhancing, are convenient for plating, obtained coating is more evenly.Time is too short
Possible calcination is not clean, overlong time, can cause the loss of graphite powder.It at this temperature, can be preferably miscellaneous except deashing etc.
Matter.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, the concentration of nitric acid described in step a
It is 30~35%, the weight ratio or volume ratio of graphite powder and nitric acid are 1 ︰ 3~4.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, and the roughening of nitric acid described in step a is
Refer to after nitric acid is added, boils 10~20min.The purpose of nitric acid roughening is mainly oxidative attack graphite powder, changes graphite particulate
Surface makes its surface form tiny hole, increases graphite surface product.
Titanium activity is strong, and under conditions of being chronically exposed to air, surface forms the oxidation of one layer of very thick densification
Film is passivated titanium and its alloy surface, it is not easy to form coating.To solve the above-mentioned problems, the present invention in the plating process,
After first cleaning to titanium alloy, surface active is carried out, activation uses acid attack.The specific steps of the acid attack activation are as follows: will
Titanium alloy keeps the temperature 2~10min in 50~100 DEG C of water, then is placed in 3~5min of immersion in acid attack liquid, cleans 2~3 times,
After drying.
Further, the acid attack liquid be mass concentration be 20~40% HF and mass concentration be 45~65%
HNO3The solution that 3~4 ︰ 1 are mixed to get by volume.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, in order to avoid introducing newly miscellaneous
Prime element, the lower impurity content the better, copper sheet purity >=99.9% described in step c.
Wherein, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, electric current when being electroplated described in step c
Density is 2.5~4.5A/dm2.Current density increases since 0, and what is just initially formed is big particle.This is primarily due to
Current density is low, and cathodic polarization effect is small, and electrode active surface position is few, therefore the formation speed of nucleus is slow.As electric current is close
The increase of degree, the crystalline structure of coating are just increasingly thinner.This is because the increase of current density, cathodic polarization effect is gradually mentioned
Height, thus caused by being continuously increased overpotential.When current density is more than the upper limit of current density, coating, which will appear, to be burnt
State, content of graphite also decline.The rate that particle is transmitted and deposited to cathode lags behind Metal electrodeposition rates, finally leads
Cause content of graphite decline.This kind of coating burnt is sometimes in spongy or normal bad colour rough surface.This may be by
In the excessive of current density, nearby there is a serious shortage of discharge metal ions for cathode, cause the sharply precipitation of hydrogen, keep the PH at this fast
Speed rises, and hydroxide or oxide is caused to be clipped in coating.Therefore, the better copper-graphite coating of performance in order to obtain, this
Current density when invention plating is with 2.5~4.5A/dm2It is advisable.
Preferably, above-mentioned TC4Titanium alloy surface is electroplated in the method for medium Copper-Graphite Composite, electrolysis time described in step c
For 20~40min.
In the present invention, it when graphite dispersion is into plating solution, is easy to be influenced by gravity and be deposited in bottom, cannot uniformly hang
It floats in the solution, influences the content of graphite in the plating solution.For this purpose, the present invention keeps stirring plating solution in the plating process, can make
Plating solution convection current is obtained, the thickness of diffusion layer is thinned, so that the discharge metal ion of anode surface when electro-deposition be made to be mended rapidly
It fills, reduces concentration polarization；Also, graphite is uniformly suspended in plating solution, is increased the probability of particle and cathode collision, is increased
The compound quantity of graphite；Stirring can also improve the online of the current density allowed, and increase operation electric current density, in turn
Increase cathodic polarization；The Surface flat of coating can also be improved, striped and orange peel shape coating are eliminated.
When stirring, mixing speed is extremely important, and when mixing speed is between 400rpm~500rpm, effect is best.When stirring
When mixing speed and being more than 500rpm, the content of graphite of deposition can decline instead.This may be to subtract since stirring forms plating solution convection current
The thickness of thin diffusion layer reduces concentration polarization so that the discharge metal ion of anode surface when electro-deposition be made to be supplemented rapidly
Change.When mixing speed is too low, uniform suspension can not be formed, also will affect the composite deposite quality of titanium alloy surface.
The present invention also provides a kind of TC prepared by the above method4Titanium alloy composite deposite.The present invention passes through electricity
The reasonable setting of parameter is plated, is cooperated, so that the binding force of titanium alloy and plating solution enhances, can be obtained in titanium electroplating surface
Uniformly, fine and close composite deposite.The composite deposite is significantly improved due to being added to graphite, wearability, is suitable for being used in aviation to navigate
It, the fields such as chemical industry and biologic medical, widened the application range of titanium alloy, remarkable in economical benefits.It is electrolysed 20~40min, plating
Layer can be used for anti-contact corrosion effect field domain with a thickness of 15~20 μm.
Explanation will be further explained to a specific embodiment of the invention by embodiment below, but do not indicated this
The protection scope of invention is limited in range described in embodiment.
Medium Copper-Graphite Composite is electroplated in titanium alloy surface with the method for the present invention in embodiment 1
By partial size 10um, density 2.2g/cm3Graphite powder, calcination 2h is activated at 380 DEG C, be added nitric acid, boil
It is roughened after boiling 15min, cleans, is dried for standby；
To TC4Titanium alloy specification is the specimen surface copper facing of 20 × 20 × 5mm, and titanium alloy and molybdenum filament are assembled
At cathode, resin is then sealed into periphery, only stays 1cm2Area be electroplated outside, so as to calculating current density.
Electrolytic parameter: by CuSO4·5H2O and H2SO4Proportion, which is carried out, according to 10 ︰ 3 of mass ratio prepares plating solution.
Implementation process: (1) first washing the grease of titanium alloy surface with gasoline, washes away the excessive greasy dirt of titanium alloy surface.So
After carry out saponification oil removing, NaOH solution is heated to 80~100 DEG C, by remove excess oil titanium alloy be put into this solution
5min carries out saponification oil removing.(2) by the titanium alloy HNO after oil removing33min is reacted in/HF solution etch.(3) it is activated:
Titanium alloy material after oil removing is put into progress impregnation 2min in HCl solution, takes out dried for standby.(4) it is electroplated: connection
Good anode and cathode material, powers on, and 15min is electroplated.Electrolysis procedure parameter: cathode-current density 4A/dm2, mixing speed is
500rpm, graphite powder concentration 40g/l.(4) composite deposite is taken out to be heat-treated.650 DEG C of heat treatment temperature, heat treatment time
3h。
Implementation result: one layer of copper/graphite composite deposite has been electroplated in titanium alloy surface, coating surface is uniform and smooth, without bright
Aobvious bubbling foaming phenomena.After bend test, coating is not separated with matrix, does not also occur coating break-off, it was demonstrated that matrix with
Binding force of cladding material is preferable.The abrasion loss that the composite deposite ability can be obtained by wear test is 0.3mm3/h。
The operating procedure of the bend test are as follows: clamp tested test piece with pliers, alternating bending 180 degree, until disconnected
It splitting, metal is not separated with matrix at this time, when with 5 times of lens examinations, though parent metal or coating are cracked, non-scale
Or fall off, coating is qualified coating.
The friction-wear test specific steps are as follows: carried out on the omnipotent friction wear testing machine of MMW-1 Li Shi, opposite grinding
Part is GCr15, and hardness number is HRC62 ± 2, and secondary friction is coating sample.After experiment, in the analysis day that precision is 0.1mg
The flat upper quality for weighing sample abrasion front and back, difference is abrasion loss.Experiment parameter setting are as follows: dry friction and wear situation, examination
Testing machine revolving speed is 100rpm, test load 50N, test period 30min.
Medium Copper-Graphite Composite is electroplated in titanium alloy surface with the method for the present invention in embodiment 2
By partial size 10um, density 2.2g/cm3Graphite powder, calcination 1h is activated at 450 DEG C, be added nitric acid, boil
It is roughened after boiling 15min, cleans, is dried for standby；
To TC4Titanium alloy specification is the specimen surface copper facing of 20 × 20 × 5mm, and titanium alloy and molybdenum filament are assembled
At cathode, resin is then sealed into periphery, only stays 1cm2Area be electroplated outside, so as to calculating current density.
Electrolytic parameter: by CuSO4·5H2O and H2SO4Proportion, which is carried out, according to 10 ︰ 3 of mass ratio prepares plating solution.
Implementation process: (1) first washing the grease of titanium alloy surface with gasoline, washes away the excessive greasy dirt of titanium alloy surface.So
After carry out saponification oil removing, NaOH solution is heated to 80 DEG C~100 DEG C, by remove excess oil titanium alloy be put into this solution
5min carries out saponification oil removing.(2) by the titanium alloy HNO after oil removing33min is reacted in/HF solution etch.(3) it is activated:
Titanium alloy material after oil removing is put into progress impregnation 2min in 60%HCl solution, takes out dried for standby.(4) it is electroplated:
Anode and cathode material is connected, is powered on, 30min is electroplated.Electrolysis procedure parameter: cathode-current density 3.5A/dm2, stirring
Speed is 400rpm, graphite powder concentration 30g/l.(4) composite deposite is taken out to be heat-treated.500 DEG C of heat treatment temperature, heat at
Manage time 2h.
Implementation result: one layer of copper/graphite composite deposite has been electroplated in titanium alloy surface, coating surface is uniform and smooth, without bright
Aobvious bubbling foaming phenomena.After bend test, coating is not separated with matrix, does not also occur coating break-off, it was demonstrated that matrix with
Binding force of cladding material is preferable.The abrasion loss that the composite deposite ability can be obtained by wear test is 0.7mm3/h。
The operating procedure of the bend test and friction-wear test is the same as embodiment 1.
Medium Copper-Graphite Composite is electroplated in titanium alloy surface with the method for the present invention in embodiment 3
By partial size 10um, density 2.2g/cm3Graphite powder, calcination 1.5h is activated at 400 DEG C, be added nitric acid,
It is roughened after boiling 15min, cleans, is dried for standby；
To TC4Titanium alloy specification is the specimen surface copper facing of 20 × 20 × 5mm, and titanium alloy and molybdenum filament are assembled
At cathode, resin is then sealed into periphery, only stays 1cm2Area be electroplated outside.
Electrolytic parameter: by CuSO4·5H2O and H2SO4Proportion, which is carried out, according to 10 ︰ 3 of mass ratio prepares plating solution.
Implementation process: (1) first washing the grease of titanium alloy surface with gasoline, washes away the excessive greasy dirt of titanium alloy surface.So
After carry out saponification oil removing, NaOH solution is heated to 80 DEG C~100 DEG C, by remove excess oil titanium alloy be put into this solution
5min carries out saponification oil removing.(2) by the titanium alloy HNO after oil removing33min is reacted in/HF solution etch.(3) it is activated:
Titanium alloy material after oil removing is put into progress impregnation 2min in HCl solution, takes out dried for standby.(4) it is electroplated: connection
Good anode and cathode material, powers on, and 60min is electroplated.Electrolysis procedure parameter: cathode-current density 2.5A/dm2, mixing speed
For 300rpm, graphite powder concentration 20g/l.(4) composite deposite is taken out to be heat-treated.450 DEG C of heat treatment temperature, when heat treatment
Between 1h.
Implementation result: one layer of copper/graphite composite deposite has been electroplated in titanium alloy surface, coating surface is uniform and smooth, without bright
Aobvious bubbling foaming phenomena.After bend test, coating is not separated with matrix, does not also occur coating break-off, it was demonstrated that matrix with
Binding force of cladding material is preferable.The abrasion loss that the composite deposite ability can be obtained by wear test is 1.1mm3/h。
The operating procedure of the bend test and friction-wear test is the same as embodiment 1.
Comparative example 4 is using existing method in the independent copper facing of titanium alloy surface
To TC4Titanium alloy specification is the specimen surface copper facing of 20 × 20 × 5mm, and titanium alloy and molybdenum filament are assembled
At cathode, resin is then sealed into periphery, only stays 1cm2Area be electroplated outside.
Electrolytic parameter: by CuSO4·5H2O and H2SO4Proportion, which is carried out, according to 10 ︰ 3 of mass ratio prepares plating solution.
Implementation process: (1) first washing the grease of titanium alloy surface with gasoline, washes away the excessive greasy dirt of titanium alloy surface.So
After carry out saponification oil removing, NaOH solution is heated to 80 DEG C~100 DEG C, by remove excess oil titanium alloy be put into this solution
5min carries out saponification oil removing.(2) by the titanium alloy HNO after oil removing33min is reacted in/HF solution etch.(3) it is activated:
Titanium alloy material after oil removing is put into progress impregnation 2min in HCl solution, takes out dried for standby.(4) it is electroplated: connection
Good anode and cathode material, powers on, and 60min is electroplated.Electrolysis procedure parameter: cathode-current density 2.5A/dm2, mixing speed
For 300rpm.(4) coating is taken out to be heat-treated.450 DEG C of heat treatment temperature, heat treatment time 1h.
Implementation result: being electroplated one layer of copper coating in titanium alloy surface, and coating surface is uniform and smooth, and nothing is significantly bubbled
Steep phenomenon.After bend test, coating is not separated with matrix, does not also occur coating break-off, it was demonstrated that matrix and binding force of cladding material
Preferably.The abrasion loss that the coating can be obtained by wear test is 1.5mm3/h。
The operating procedure of the bend test and friction-wear test is the same as embodiment 1.
The result and embodiment 3 of comparative example 4 compare it is found that under identical process conditions, are electroplated, are answered after graphite is added
The abrasion loss for closing coating is 1.1mm3/ h illustrates that graphite, which is added, is plated to composite deposite, can be improved the wearability of material.
Medium Copper-Graphite Composite is electroplated in titanium alloy surface using existing method in comparative example 5
By partial size 10um, density 2.2g/cm3Graphite powder, 1~2h of calcination is activated at 380~450 DEG C, is added
Enter nitric acid, be roughened after boiling, cleans, is dried for standby；
To TC4The specimen surface that titanium alloy specification is 20 × 20 × 5mm plates medium Copper-Graphite Composite, by titanium alloy
It carries out being assembled into cathode with molybdenum filament, resin is then sealed into periphery, only stays 1cm2Area be electroplated outside.
Electrolytic parameter: by CuSO4·5H2O and H2SO4Proportion, which is carried out, according to 10 ︰ 3 of mass ratio prepares plating solution.
Implementation process: (1) titanium alloy is directly electroplated titanium alloy without processing；Anode and cathode material is connected, is connect
60min is electroplated in energization source.Electrolysis procedure parameter: cathode-current density 2.5A/dm2, mixing speed 300rpm.(2) it takes
Coating is heat-treated out.450 DEG C of heat treatment temperature, heat treatment time 1h.
Implementation result: being electroplated one layer very thin of copper-graphite coating in titanium alloy surface, and coating surface is coarse, rough,
There is apparent bubbling foaming phenomena.After bend test, coating separates disengaging with matrix, and matrix is bad with binding force of cladding material.
Claims (10)
1.TC4The method of titanium alloy surface plating medium Copper-Graphite Composite, which comprises the following steps:
A, by graphite powder calcination, nitric acid roughening is added, cleans, drying for standby；Copper-bath and sulfuric acid solution are mixed to form
Electroplate liquid graphite is added in electroplate liquid, makes 180~200g/l of concentration of copper sulfate in electroplate liquid, sulfuric acid concentration for 40~
60g/l, graphite concentration are 20~40vol%；
B, to TC4Titanium alloy surface oil removal treatment, then acid attack activation is carried out, it cleans, drying for standby；
C, electroplate liquid is added in electrolytic cell, the titanium alloy that step b is obtained is assembled into cathode with metal molybdenum filament, copper sheet is sun
Electroplate liquid is stirred in pole, is electrolysed 10~60min at normal temperature, is then electroplated to obtain copper-graphite composite deposite in titanium alloy surface.
2. TC according to claim 14The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: step
The temperature of calcination described in rapid a is 380~450 DEG C, and calcination time is 1~2h.
3. TC according to claim 14The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: step
The concentration of nitric acid described in rapid a is 30~35%, and the weight ratio or volume ratio of graphite powder and nitric acid are 1 ︰ 3~4.
4. TC according to claim 14The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: step
The concrete operations of oil removal treatment described in rapid b are as follows: titanium alloy is cleaned using acetone or gasoline, places into 80~100 DEG C of NaOH
5~10min of middle immersion.
5. TC according to claim 14The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: step
The specific steps of acid attack activation described in rapid b are as follows: titanium alloy is kept the temperature into 2~10min in 50~80 DEG C of water, then is placed in acid
In etchant impregnate 3~5min, place into HCl solution impregnate 2~5min to get.
6. TC according to claim 54The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: institute
The HNO that the acid attack liquid stated is the HF that mass concentration is 20~40% and mass concentration is 45~65%33~4 ︰ 1 by volume
The solution being mixed to get.
7. TC according to claim 14The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: step
The speed of stirring described in rapid c is 400~500rpm.
8. TC according to claim 14The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: step
Current density is 2.5~4.5A/dm when being electroplated described in rapid c2。
9. TC according to claim 14The method of titanium alloy surface plating medium Copper-Graphite Composite, it is characterised in that: step
Electrolysis time described in rapid c is 20~40min.
10. the TC that method according to any one of claims 1 to 9 is prepared4Titanium alloy composite deposite.
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