CN104018145B - A kind of preparation method of titanium alloy surface graphene film - Google Patents
A kind of preparation method of titanium alloy surface graphene film Download PDFInfo
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- CN104018145B CN104018145B CN201410257712.1A CN201410257712A CN104018145B CN 104018145 B CN104018145 B CN 104018145B CN 201410257712 A CN201410257712 A CN 201410257712A CN 104018145 B CN104018145 B CN 104018145B
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Abstract
The invention discloses the preparation method of a kind of titanium alloy surface graphene film, concrete steps include: carry out putting in piranha solution by medical titanium alloy and carry out hydroxylating process, are then placed in self assembly Silan-based Thin Films in amino silane solution；Graphene oxide powder ultrasonic is processed as stable graphene oxide colloid；Surface is immersed in graphene oxide colloid with the titanium alloy of Silan-based Thin Films and prepares silane oxidation graphene film；Finally utilize halogen acids oxidation graphene film, obtain redox graphene laminated film after drying.Present invention process method is simple, and to experiment operator non-hazardous, prepared film integrity is good, and intensity is high, and coefficient of friction is low, excellent in abrasion resistance, is expected to become Medical joint material.
Description
Technical field
The invention belongs to titanium alloy material performance improvement technical field, relate to one and prepare thin film to carry at titanium alloy surface
The method of titanium master alloy Tribological Properties.
Background technology
Titanium alloy, because having good comprehensive mechanical performance and etch resistant properties, is widely used in aerospace, oil
The fields such as chemical industry.Owing to titanium alloy has good biocompatibility, higher specific strength and excellent anti-fatigue performance,
The elastic modelling quantity adding it relatively low is near with bone photo, it is possible to effectively by the healthy bone of load transfer to surrounding, can be by
Titanium alloy is used for joint bone material.
But owing to the chemical affinity of titanium is bigger, easily produce at friction surface and adhere to, cause coefficient of friction to increase.Titanium
The titanium oxide that alloy surface is formed wears no resistance, and easily peels off in friction process, the abrasive wear in aggravation joint.With
Time substantial amounts of metal ion concentration at periarticular, the biochemical reaction of easy exception throw, cause joint mobilization to lose
Effect.Therefore, it is necessary to titanium alloy surface is modified, to improve its frictional behaviour.
Graphene is that carbon atom passes through sp2The single thin film of the hexagonal cell lattice that orbital hybridization is formed.It is
The thinnest is also the hardest nano material, has huge specific surface area (2600m2/ g) and specific strength (anti-
Tensile strength 125GPa), taller upper 100 times of the iron and steel that its strength ratio is the most best, be in known materials intensity and
The crystal structure that hardness is the highest.And Graphene light weight, wearability and corrosion-resistant good, excellent thermal conductivity.
By can greatly reduce coefficient of friction at titanium alloy surface deposited graphite alkene thin film, improve wearability, improve
Its biological friction performance.But Graphene itself is more stable, if directly depositing thin film at titanium alloy surface, so
Adhesion between matrix and thin film is strong not, and the thin film of formation easily comes off in friction process.
Therefore, those skilled in the art is devoted to develop a kind of by silane and the graphene oxide containing active function groups
Reaction, in the method that titanium alloy surface prepares silane-graphene composite thin film, to improve the tribology of titanium alloy
Energy.
Summary of the invention
The purpose of the present invention overcomes the defect in terms of above-mentioned titanium alloy frictional behaviour to provide a kind of titanium alloy surface system
The method of standby graphene film, has relatively low coefficient of friction by the method at thin film prepared by titanium alloy surface,
The tribological property of titanium alloy can be greatly enhanced.
For achieving the above object, the invention provides the preparation method of a kind of titanium alloy surface graphene film, the present invention
Technical scheme be divided into three phases, the most at room temperature the titanium alloy sheet surface of polishing is carried out hydroxyl
Change pretreatment, then prepare graphene oxide film by self-assembling method at titanium alloy surface, finally will oxidation
Graphene film carries out reduction treatment.Concrete scheme comprises the steps:
A. the titanium alloy after surface finish being processed is put in aqueous isopropanol ultrasonic, then with ultrapure water, then delays
Slow play enters in piranha solution to stand, and the titanium alloy after processing after taking-up is put in new piranha solution and carried out two
Secondary standing, makes titanium alloy surface hydroxylating；Ultra-pure water used by the present invention refers to that resistivity is more than 18M Ω cm (25 DEG C
Time) water.
B., after the titanium alloy after hydroxylating being cleaned with deionized water, insert in amino silane solution；
C. putting in appropriate distilled water by graphene oxide powder, ultrasound wave disperses, and obtains stable graphene oxide glue
Body；
D. the titanium alloy after described step b processes is immersed in the graphene oxide colloid that described step c obtains,
Hermetic container persistently keeps constant temperature；
E. the titanium alloy after described step d processes is immersed in the mixed solution of halogen acids and phosphoric acid, at hermetic container
Middle heating；
F. the product with deionized water obtained through described step e process is rinsed repeatedly, until the pH value of solution after Chong Xiing
For neutrality, the product drying after then rinsing.
Preferably, in above-mentioned steps a: titanium alloy comprises selected from Ti6Al4V、Ti6Al7Nb and Ti12Mo5One in Ta；
The concentration of isopropanol is by mass percentage 70%；Piranha solution be by mass percentage concentration be 98% dense
Sulphuric acid and by mass percentage concentration are the solution of the hydrogen peroxide 7:3 by volume mixing of 30%；Titanium alloy is in isopropyl
Time ultrasonic in alcoholic solution is 30～60min；It it is 3～5 times with ultrapure water number of times；In piranha solution first
Time of repose is 10～30min；Secondary time of repose is 5～10min.
Preferably, in above-mentioned steps b, amino silane solution be the toluene to mix by 5:1 volume ratio and water as solvent,
So that γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is for solute, the concentration of solute is 0.5～2mmol/L；Use deionization
The number of times that water cleans is 3～5 times；The titanium alloy after the hydroxylating storing time in amino silane Solutions Solution is
2～12h.
Preferably, the ultrasonic dispersing time in above-mentioned steps c is 30min～2h；The described graphene oxide glue obtained
The concentration of body is 0.1～2mg/ml.
Preferably, in above-mentioned steps d, the steady temperature scope of hermetic container is 40～80 DEG C, the constant temperature persistent period is
10～24h.
Preferably, in above-mentioned steps e, halogen acids be by mass percentage concentration be 30%～57% HI solution or
Concentration is the HBr solution of 30%～47% by mass percentage, and mixed solution refers to described halogen acids and by quality hundred
Proportion by subtraction meter concentration is the solution that mixes by 9:1 volume ratio of phosphoric acid of 30%；Titanium alloy heating in hermetic container time
Between be 20min～10h, heating and temperature control is at 40～100 DEG C.
Preferably, the described dry finger in above-mentioned steps f places 24h in 40 DEG C of vacuum.
Present invention also offers prepare in aforementioned manners containing oxidation graphene film titanium alloy material.
Compared to prior art, beneficial effects of the present invention is embodied in:
The present invention first uses the graphene oxide containing active function groups, utilizes silane coupler to prepare graphene oxide certainly
Component film, then obtain that there is high intensity and the reduction-oxidation graphite of tribological property excellence through hydrogen halides method of reducing
Alkene thin film, the thin film of preparation has relatively low coefficient of friction.The present invention has that technique is simple, low cost, efficiency high,
The features such as environmentally safe.
Compare employing H2N4·H2O and NaBH4Deng method of reducing, the method reaction that the present invention uses is gentle, whole
Process will not produce harm to operator；The graphene film defect of preparation is few, will not resolve into fractionlet,
Good integrity can be kept；And reduction reaction will not produce big shadow to the combination between thin film and matrix
Ring, there is good interface binding power, titanium alloy friction and wear behavior can be obviously improved.The final thin film obtained
Its intensity, elasticity, bio-tribology performance and wearability are more preferable, are expected to become Medical joint material, thus have
There is the biggest using value.
Below with reference to accompanying drawing, the technique effect of design, concrete structure and the generation of the present invention is described further, with
It is fully understood from the purpose of the present invention, feature and effect.
Accompanying drawing explanation
Fig. 1 is schematic diagram of the present invention；
Fig. 2 is the SEM figure of the titanium alloy redox graphene laminated film that the embodiment of the present invention 1 obtains.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polishing6Al4V puts into ultrasonic 30min in 70% aqueous isopropanol, here
Ti6Al4V also can use Ti6Al7Nb or Ti12Mo5Ta substitutes；Use ultrapure water 5 times again, the most slowly put into
10min in piranha solution, after taking-up again will process after titanium alloy put into 5min in new piranha solution,
Make titanium alloy surface hydroxylating.
B., after hydroxylated titanium alloy deionized water being cleaned 5 times, putting into propyl trimethoxy silicane content is
Self assembly Silan-based Thin Films in the amino silane solution of 2mmol/L, the time is 2h.
C. putting in distilled water by graphene oxide powder, ultrasound wave dispersion 30min, obtaining concentration is 0.1mg/mL
Stable graphene oxide colloid.
D. graphene oxide colloid is immersed with the titanium alloy of silane in surface, hermetic container keeps constant temperature
80 DEG C continue 10h, by silane and the reaction of graphene oxide, are just prepared for silane-oxidation at titanium alloy surface
Graphene composite film.
E. the titanium alloy with graphene oxide film is immersed 55%HI and the mixed solution (v/v=of 30% phosphoric acid
9:1), heating 20min in hermetic container, temperature controls at 100 DEG C.By nucleophilic substitution by titanium alloy
The graphene oxide on surface reduces.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing is neutrality, then will
Product after flushing places 24h in 40 DEG C of vacuum, prepares titanium alloy surface redox graphene laminated film.
Testing the titanium alloy surface redox graphene laminated film of preparation, result is as follows:
Using multifunction electronic energy disperse spectroscopy (XPS) to analyze the chemical composition of composite membrane, high definition C1s peak display titanium closes
Having assembled graphene oxide on gold, after reduction, the hydroxyl on graphene oxide, epoxy radicals and carboxyl disappear
?.Use scanning electron microscope (SEM) that the surface topography of composite membrane is analyzed, as in figure 2 it is shown, SEM figure
Display oxidation graphene film has successfully been assembled in titanium alloy surface.With UMT-2MT type frictional testing machine
Recording laminated film coefficient of friction when load is 0.1N and sliding velocity is 1Hz is about 0.12, and the most multiple
Close the titanium alloy T i of film6Al4V coefficient of friction is 0.45, it can be seen that laminated film demonstrates good tribology
Energy.
Embodiment 2
The preparation method of a kind of titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polishing6Al4V puts into ultrasonic 60min in 70% aqueous isopropanol, here
Ti6Al4V also can use Ti6Al7Nb or Ti12Mo5Ta substitutes, then with ultrapure water 3 times, the most slowly puts into
30min in piranha solution, after taking-up again will process after titanium alloy put into 10min in new piranha solution,
Make titanium alloy surface hydroxylating.
B., after hydroxylated titanium alloy deionized water being cleaned 5 times, putting into propyl trimethoxy silicane content is
Self assembly Silan-based Thin Films in the amino silane solution of 0.5mmol/L, the time is 12h.
C. putting in distilled water by graphene oxide powder, ultrasound wave dispersion 2h, obtaining concentration is that 2mg/mL is steady
Fixed graphene oxide colloid.
D. graphene oxide colloid is immersed with the titanium alloy of silane in surface, hermetic container keeps constant temperature
40 DEG C continue 24h, by silane and the reaction of graphene oxide, are just prepared for silane-oxidation at titanium alloy surface
Graphene composite film.
E. the titanium alloy with graphene oxide film is immersed 30%HI and the mixed solution (v/v of 30% phosphoric acid
=9:1), hermetic container heats 10h, temperature controls at 40 DEG C.By nucleophilic substitution by titanium alloy table
The graphene oxide in face reduces.
F. the product with deionized water after reduction is rinsed until the pH value of solution after rinsing is neutrality repeatedly, then will punching
Product after washing places 24h in 40 DEG C of vacuum, prepares titanium alloy surface redox graphene laminated film.
Testing the titanium alloy surface redox graphene laminated film of preparation, result is as follows:
Using multifunction electronic energy disperse spectroscopy (XPS) to analyze the chemical composition of composite membrane, high definition C1s peak display titanium closes
Having assembled graphene oxide on gold, after reduction, the hydroxyl on graphene oxide, epoxy radicals and carboxyl disappear
?.Record laminated film with UMT-2MT type frictional testing machine to rub when load is 0.1N and sliding velocity is 1Hz
Wiping coefficient is about 0.16, and does not has the titanium alloy T i of composite membrane6Al4V coefficient of friction is 0.45, it can be seen that multiple
Close thin film and demonstrate good tribological property.
Embodiment 3
The preparation method of a kind of titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polishing6Al4V puts into ultrasonic 45min in 70% aqueous isopropanol, here
Ti6Al4V also can use Ti6Al7Nb or Ti12Mo5Ta substitutes, then with ultrapure water 3 times, the most slowly puts into piranha
20min in solution, the titanium alloy after again processing after taking-up is put into 5min in new piranha solution, is made titanium alloy
Surface hydroxylation.
B., after hydroxylated titanium alloy deionized water being cleaned 3 times, putting into propyl trimethoxy silicane content is
Self assembly Silan-based Thin Films in the amino silane solution of 2mmol/L, the time is 2h.
C. putting in distilled water by graphene oxide powder, ultrasound wave dispersion 30min, obtaining concentration is 0.1mg/mL
Stable graphene oxide colloid.
D. graphene oxide colloid is immersed with the titanium alloy of silane in surface, keep constant temperature 60 DEG C to hold in hermetic container
Continuous 16h, by silane and the reaction of graphene oxide, is just prepared for silane-graphene oxide at titanium alloy surface and is combined
Thin film.
E. the titanium alloy with graphene oxide film is immersed 45%HBr and the mixed solution (v/v=of 30% phosphoric acid
9:1), heating 30min in hermetic container, temperature controls at 100 DEG C.By nucleophilic substitution by titanium alloy surface
Graphene oxide reduce.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing is neutrality, then will rinse
After product in 40 DEG C of vacuum, place 24h, prepare titanium alloy surface redox graphene laminated film.
Embodiment 4
The preparation method of a kind of titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polishing6Al4V puts into ultrasonic 45min, Ti here in 70% isopropyl solution6Al4V
Also Ti can be used6Al7Nb or Ti12Mo5Ta substitutes, then with ultrapure water 3 times, the most slowly puts in piranha solution
20min, the titanium alloy after again processing after taking-up is put into 5min in new piranha solution, is made titanium alloy surface hydroxyl
Base.
B., after hydroxylated titanium alloy deionized water being cleaned 3 times, putting into propyl trimethoxy silicane content is
Self assembly Silan-based Thin Films in the amino silane solution of 1mmol/L, the time is 2h.
C. putting in distilled water by graphene oxide powder, ultrasound wave dispersion 30min, obtaining concentration is 1.0mg/mL
Stable graphene oxide colloid.
D. graphene oxide colloid is immersed with the titanium alloy of silane in surface, keep constant temperature 60 DEG C to hold in hermetic container
Continuous 16h, by silane and the reaction of graphene oxide, is just prepared for silane-graphene oxide at titanium alloy surface and is combined
Thin film.
E. the titanium alloy with graphene oxide film is immersed 30%HI and the mixed solution (v/v=of 30% phosphoric acid
9:1), heating 30min in hermetic container, temperature controls at 100 DEG C.By nucleophilic substitution by titanium alloy surface
Graphene oxide reduce.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing is neutrality, then will rinse
After product in 40 DEG C of vacuum, place 24h, prepare titanium alloy surface redox graphene laminated film.
Embodiment 5
The preparation method of a kind of titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polishing6Al4V puts into ultrasonic 45min, Ti here in 70% isopropyl solution6Al4V
Also Ti can be used6Al7Nb or Ti12Mo5Ta substitutes, then with ultrapure water 3 times, the most slowly puts in piranha solution
20min, the titanium alloy after again processing after taking-up is put into 5min in new piranha solution, is made titanium alloy surface hydroxyl
Base.
B., after hydroxylated titanium alloy deionized water being cleaned 3 times, putting into propyl trimethoxy silicane content is
Self assembly Silan-based Thin Films in the amino silane solution of 1mmol/L, the time is 2h.
C. putting in distilled water by graphene oxide powder, ultrasound wave dispersion 30min, obtaining concentration is 1.0mg/mL
Stable graphene oxide colloid.
D. graphene oxide colloid is immersed with the titanium alloy of silane in surface, keep constant temperature 60 DEG C to hold in hermetic container
Continuous 16h, by silane and the reaction of graphene oxide, is just prepared for silane-graphene oxide at titanium alloy surface and is combined
Thin film.
E. the titanium alloy with graphene oxide film is immersed 57%HI and the mixed solution (v/v=of 30% phosphoric acid
9:1), heating 30min in hermetic container, temperature controls at 100 DEG C.By nucleophilic substitution by titanium alloy surface
Graphene oxide reduce.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing is neutrality, then will rinse
After product in 40 DEG C of vacuum, place 24h, prepare titanium alloy surface redox graphene laminated film.
Embodiment 6
The preparation method of a kind of titanium alloy surface graphene film, comprises the following steps:
Raw material used includes: the graphene oxide powder that certain company produces.
A. by the titanium alloy T i of polishing6Al4V puts into ultrasonic 45min, Ti here in 70% isopropyl solution6Al4V
Also Ti can be used6Al7Nb or Ti12Mo5Ta substitutes, then with ultrapure water 3 times, the most slowly puts in piranha solution
20min, the titanium alloy after again processing after taking-up is put into 5min in new piranha solution, is made titanium alloy surface hydroxyl
Base.
B., after hydroxylated titanium alloy deionized water being cleaned 3 times, putting into propyl trimethoxy silicane content is
Self assembly Silan-based Thin Films in the amino silane solution of 1mmol/L, the time is 2h.
C. putting in distilled water by graphene oxide powder, ultrasound wave dispersion 30min, obtaining concentration is 1.0mg/mL
Stable graphene oxide colloid.
D. graphene oxide colloid is immersed with the titanium alloy of silane in surface, keep constant temperature 60 DEG C to hold in hermetic container
Continuous 16h, by silane and the reaction of graphene oxide, is just prepared for silane-graphene oxide at titanium alloy surface and is combined
Thin film.
E. the titanium alloy with graphene oxide film is immersed 47%HBr and the mixed solution (v/v=of 30% phosphoric acid
9:1), heating 30min in hermetic container, temperature controls at 100 DEG C.By nucleophilic substitution by titanium alloy surface
Graphene oxide reduce.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing is neutrality, then will rinse
After product in 40 DEG C of vacuum, place 24h, prepare titanium alloy surface redox graphene laminated film.
Testing the titanium alloy surface redox graphene laminated film of preparation, result is as follows:
Multifunction electronic energy disperse spectroscopy (XPS) is used to analyze the chemical composition of composite membrane, on high definition C1s peak display titanium alloy
Graphene oxide in assembling, after reduction, hydroxyl, epoxy radicals and carboxyl on graphene oxide disappear.With
UMT-2MT type frictional testing machine records laminated film coefficient of friction when load is 0.1N and sliding velocity is 1Hz
About 0.14, and there is no the titanium alloy T i of composite membrane6Al4V coefficient of friction is 0.45, illustrates that redox graphene is multiple
Closing thin film and be successfully assembled in titanium alloy surface, thin film has outstanding tribological property and good interface binding power,
The tribological property of titanium alloy significantly improves.
The preferred embodiment of the present invention described in detail above.Should be appreciated that those of ordinary skill in the art without
Need creative work just can make many modifications and variations according to the design of the present invention.Therefore, all in the art
Technical staff the most on the basis of existing technology can by logical analysis, reasoning, or a limited experiment
With the technical scheme obtained, all should be in the protection domain being defined in the patent claims.
Claims (8)
1. the preparation method of a titanium alloy surface graphene film, it is characterised in that comprise the steps:
A. the titanium alloy after surface finish being processed is put in aqueous isopropanol ultrasonic, then with ultrapure water, then delays
Slow play enters in piranha solution to stand, and the titanium alloy after standing being processed takes out and places in new piranha solution
Row secondary stands, and makes titanium alloy surface hydroxylating；
B., after the titanium alloy after hydroxylating being cleaned with deionized water, insert in amino silane solution；
C. putting in distilled water by graphene oxide powder, ultrasound wave disperses, and obtains graphene oxide colloid；
D. the titanium alloy after described step b processes is immersed in the graphene oxide colloid that described step c obtains,
Hermetic container persistently keeps constant temperature；
E. the titanium alloy after described step d processes is immersed in the mixed solution of halogen acids and phosphoric acid, at hermetic container
Middle heating；
F. the product with deionized water obtained through described step e process is rinsed repeatedly, until the pH value of solution after Chong Xiing
For neutrality, the product drying after then rinsing.
2. the preparation method of a titanium alloy surface graphene film according to claim 1, it is characterised in that
In described step a: described titanium alloy is selected from Ti6Al4V、Ti6Al7Nb and Ti12Mo5One in Ta；Described isopropyl
The concentration of alcohol is by mass percentage 70%；Described piranha solution is that concentration is 98% by mass percentage
Concentrated sulphuric acid and by mass percentage concentration are the solution of the hydrogen peroxide 7:3 by volume mixing of 30%.
3. the preparation method of a titanium alloy surface graphene film according to claim 2, it is characterised in that
In described step a: described titanium alloy time ultrasonic in aqueous isopropanol is 30～60min；With ultrapure water
Number is 3～5 times；In piranha solution, time of repose is 10～30min first；Secondary time of repose is 5～10min.
4. the preparation method of a titanium alloy surface graphene film according to claim 1, it is characterised in that:
Ultrasonic dispersing time in described step c is 30min～2h；The concentration of the described graphene oxide colloid obtained is
0.1～2mg/ml.
5. the preparation method of a titanium alloy surface graphene film according to claim 1, it is characterised in that:
In described step d, the steady temperature scope of described hermetic container is 40～80 DEG C, the constant temperature persistent period is 10～24h.
6. the preparation method of a titanium alloy surface graphene film according to claim 1, it is characterised in that:
In described step e, described halogen acids is that concentration is the HI solution of 30%～57% or by quality hundred by mass percentage
Proportion by subtraction meter concentration is the HBr solution of 30%～47%, and mixed solution refers to described halogen acids and the denseest
Degree is the solution that mixes by 9:1 volume ratio of phosphoric acid of 30%.
7. the preparation method of a titanium alloy surface graphene film according to claim 6, it is characterised in that:
In described step e, the time of titanium alloy heating in hermetic container is 20min～10h, and heating and temperature control exists
40～100 DEG C；Described dry finger in described step f places 24h in 40 DEG C of vacuum.
8. one kind utilizes graphene-containing thin film titanium alloy material prepared by method as according to any one of claim 1 to 7
Material.
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