CN104018145A - Method for preparing graphene film on surface of titanium alloy - Google Patents
Method for preparing graphene film on surface of titanium alloy Download PDFInfo
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- CN104018145A CN104018145A CN201410257712.1A CN201410257712A CN104018145A CN 104018145 A CN104018145 A CN 104018145A CN 201410257712 A CN201410257712 A CN 201410257712A CN 104018145 A CN104018145 A CN 104018145A
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Abstract
The invention discloses a method for preparing a graphene film on the surface of titanium alloy. The method specifically comprises the following steps of putting a medical titanium alloy into a piranha solution and carrying out hydroxylation treatment, and then putting into an amino silane solution, and self-assembling a silane film; carrying out ultrasonic treatment on graphene oxide powder to obtain a stable graphene oxide colloid; immersing the titanium alloy of which the surface is attached with the silane film in the graphene oxide colloid to prepare a silane-graphene oxide film; and finally, reducing the graphene oxide film with hydrogen halide acid, and drying to obtain the reduced graphene oxide composite film. The method disclosed by the invention is simple and causes no harm to experiment operators, and the obtained film has the advantages of good integrity, high strength, low coefficient of friction and excellent wear resistance and is expected to become a medical joint material.
Description
Technical field
The invention belongs to titanium alloy material improvement in performance technical field, relate to and a kind ofly at titanium alloy surface, prepare film to improve the method for titanium alloy surface tribological property.
Background technology
Titanium alloy, because having good comprehensive mechanical performance and etch resistant properties, is widely used in aerospace, field of petrochemical industry.Because titanium alloy has good biocompatibility, higher specific tenacity and good anti-fatigue performance, add its lower Young's modulus and bone photo near, can be effectively by load transfer to healthy bone around, can be by titanium alloy for articular bone material.
But because the chemical affinity of titanium is larger, easily at friction surface, produce and adhere to, cause frictional coefficient to increase.The titanium oxide that titanium alloy surface forms wears no resistance, and easily peels off the abrasive wear in aggravation joint in friction process.A large amount of metal ions is gathered in periarticular simultaneously, and easily the biochemical reaction of exception throw, causes joint mobilization to lose efficacy.Therefore, must carry out modification to titanium alloy surface, to improve its frictional behaviour.
Graphene is that carbon atom passes through sp
2the single thin film of the sexangle honeycomb lattice that orbital hybridization forms.It is the thinnest in the world be up to now also the hardest nano material, there is huge specific surface area (2600m
2/ g) and specific tenacity (tensile strength 125GPa), its strength ratio is taller upper 100 times of best iron and steel in the world, is intensity and the highest crystalline structure of hardness in known materials.And Graphene quality is light, wear resistance and corrosion-resistant good, heat conductivility is excellent.
By can greatly reducing frictional coefficient at titanium alloy surface deposition graphene film, improve wear resistance, improve its biological friction performance.But Graphene itself is more stable, if directly at titanium alloy surface deposit film, the bonding force between matrix and film is strong not like this, and the 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 graphite oxide alkene reaction that contains active function groups, prepares the method for silane-graphene composite thin film, to improve the tribological property of titanium alloy at titanium alloy surface.
Summary of the invention
Object of the present invention overcomes the defect of above-mentioned titanium alloy frictional behaviour aspect and provides a kind of titanium alloy surface to prepare the method for graphene film, the film of preparing at titanium alloy surface by the method has lower frictional coefficient, can greatly improve the tribological property of titanium alloy.
For achieving the above object, the invention provides a kind of preparation method of titanium alloy surface graphene film, technical scheme of the present invention is divided into three phases, first at room temperature hydroxylation pre-treatment is carried out in the titanium alloy sheet surface of polished finish, then by self-assembling method, at titanium alloy surface, prepare graphene oxide film, finally graphene oxide film is reduced to processing.Concrete scheme comprises the steps:
A. it is ultrasonic that the titanium alloy after surface finish being processed is put into aqueous isopropanol, with ultrapure water, rinse again, then slowly put into piranha solution standing, after taking-up, the titanium alloy after processing being put into new piranha solution, to carry out secondary standing, makes titanium alloy surface hydroxylation; The present invention's ultrapure water used refers to that resistivity is greater than the water of 18M Ω cm (25 ℃ time).
B. by the titanium alloy after hydroxylation with after washed with de-ionized water, insert in aminosilane solution;
C. graphene oxide powder is put into appropriate distilled water, ultrasonic wave is disperseed, and obtains stable graphene oxide colloid;
D. the titanium alloy after described step b processes is immersed in the graphene oxide colloid that described step c obtains, in encloses container, continue to keep constant temperature;
E. the titanium alloy after described steps d is processed is immersed in the mixing solutions of haloid acid and phosphoric acid, in encloses container, heat;
F. by processing through described step e the product with deionized water obtaining, repeatedly rinse, until the pH value of solution after rinsing is neutral, then by the product drying after rinsing.
Preferably, in above-mentioned steps a: titanium alloy comprises and is selected from Ti
6al
4v, Ti
6al
7nb and Ti
12mo
5a kind of in Ta; The concentration of Virahol is by mass percentage 70%; Piranha solution is the vitriol oil that concentration is 98% by mass percentage and the hydrogen peroxide solution that 7:3 mixes by volume that concentration is 30% by mass percentage; Titanium alloy ultrasonic time in aqueous isopropanol is 30～60min; With ultrapure water washing time, it is 3～5 times; In piranha solution, time of repose is 10～30min first; Secondary time of repose is 5～10min.
Preferably, in above-mentioned steps b, aminosilane solution is that take by toluene and the water of the mixing of 5:1 volume ratio is solvent, and so that γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is for solute, the concentration of solute is 0.5～2mmol/L; With the number of times of washed with de-ionized water, it is 3～5 times; The storing time of titanium alloy after hydroxylation in aminosilane solution solution is 2～12h.
Preferably, the ultrasonic wave jitter time in above-mentioned steps c is 30min～2h; The concentration of the described graphene oxide colloid obtaining is 0.1～2mg/ml.
Preferably, in above-mentioned steps d, the steady temperature scope of encloses container is that 40～80 ℃, constant temperature time length are 10～24h.
Preferably, in above-mentioned steps e, haloid acid is the HI solution that concentration is 30%～57% by mass percentage or the HBr solution that concentration is 30%～47% by mass percentage, and mixing solutions refers to the solution that described haloid acid and the phosphoric acid that concentration is 30% by mass percentage mix by 9:1 volume ratio; The time of the heating of titanium alloy in encloses container is 20min～10h, and heating and temperature control is at 40～100 ℃.
Preferably, the described dry finger in above-mentioned steps f is placed 24h in 40 ℃ of vacuum.
The present invention also provide with aforesaid method, prepare containing oxidation graphene film titanium alloy material.
Than prior art, beneficial effect of the present invention is embodied in:
The present invention first adopts the graphene oxide that contains active function groups, utilize silane coupling agent to prepare graphene oxide self-assembled film, through hydrogen halide method of reducing, obtain having again the oxidation graphene film of high strength and tribological property excellence, the film of preparation has lower frictional coefficient.The present invention has the features such as technique is simple, cost is low, efficiency is high, environmentally safe.
Compare and adopt H
2n
4h
2o and NaBH
4deng method of reducing, the method reaction temperature that the present invention adopts and, whole process can not produce harm to operator; The graphene film defect of preparation is few, can not resolve into small shreds, can keep good integrity; And reduction reaction can not produce large impact on the combination between film and matrix, there is good interface binding power, can obviously improve titanium alloy friction and wear behavior.Final its intensity of film, elasticity, bio-tribology performance and the wear resistance obtaining is better, is expected to become Medical joint material, thereby has very large using value.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object 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 of the embodiment of the present invention 1 acquisition.
Embodiment
Embodiment 1
A preparation method for titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polished finish
6al
4v puts into the ultrasonic 30min of 70% aqueous isopropanol, the Ti here
6al
4v is available Ti also
6al
7nb or Ti
12mo
5ta substitutes; With ultrapure water, rinse 5 times again, then slowly put into piranha solution 10min, after taking-up, again the titanium alloy after processing is put into new piranha solution 5min, make titanium alloy surface hydroxylation.
B. by after hydroxylated titanium alloy use washed with de-ionized water 5 times, putting into propyl trimethoxy silicane content is the aminosilane solution self-assembly Silan-based Thin Films of 2mmol/L, and the time is 2h.
C. graphene oxide powder is put into distilled water, ultrasonic wave is disperseed 30min, and obtaining concentration is the graphene oxide colloid that 0.1mg/mL is stable.
D. the titanium alloy immersion graphene oxide colloid with silane by surface keeps 80 ℃ of lasting 10h of constant temperature in encloses container, by the reaction of silane and graphene oxide, at titanium alloy surface, has just prepared silane-graphene composite thin film.
E. the titanium alloy with graphene oxide film is immersed to the mixing solutions (v/v=9:1) of 55%HI and 30% phosphoric acid, heat 20min in encloses container, temperature is controlled at 100 ℃.By nucleophilic substitution reaction, the graphene oxide of titanium alloy surface is reduced.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing, for neutral, is then placed 24h by the product after rinsing in 40 ℃ of vacuum, makes titanium alloy surface redox graphene laminated film.
Titanium alloy surface redox graphene laminated film to preparation is tested, and result is as follows:
Adopt multifunction electronic energy spectrometer (XPS) to analyze the chemical composition of composite membrane, high definition C1s peak shows on titanium alloy has assembled graphene oxide, and hydroxyl, epoxy group(ing) and carboxyl after reduction on graphene oxide have disappeared.Adopt scanning electron microscope (SEM) to analyze the surface topography of composite membrane, as shown in Figure 2, SEM figure shows that oxidation graphene film has successfully been assembled in titanium alloy surface.With UMT-2MT type frictional testing machines record laminated film load be 0.1N and slip velocity while being 1Hz frictional coefficient be 0.12 left and right, and there is no the titanium alloy T i of composite membrane
6al
4v frictional coefficient is 0.45, can see that laminated film demonstrates good tribological property.
Embodiment 2
A preparation method for titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polished finish
6al
4v puts into the ultrasonic 60min of 70% aqueous isopropanol,, the Ti here
6al
4v is available Ti also
6al
7nb or Ti
12mo
5ta substitutes, then rinses 3 times with ultrapure water, then slowly puts into piranha solution 30min, after taking-up, again the titanium alloy after processing is put into new piranha solution 10min, makes titanium alloy surface hydroxylation.
B. by after hydroxylated titanium alloy use washed with de-ionized water 5 times, putting into propyl trimethoxy silicane content is the aminosilane solution self-assembly Silan-based Thin Films of 0.5mmol/L, and the time is 12h.
C. graphene oxide powder is put into distilled water, ultrasonic wave is disperseed 2h, and obtaining concentration is the graphene oxide colloid that 2mg/mL is stable.
D. the titanium alloy immersion graphene oxide colloid with silane by surface keeps 40 ℃ of lasting 24h of constant temperature in encloses container, by the reaction of silane and graphene oxide, at titanium alloy surface, has just prepared silane-graphene composite thin film.
E. the titanium alloy with graphene oxide film is immersed to the mixing solutions (v/v=9:1) of 30%HI and 30% phosphoric acid, heat 10h in encloses container, temperature is controlled at 40 ℃.By nucleophilic substitution reaction, the graphene oxide of titanium alloy surface is reduced.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing, for neutral, is then placed 24h by the product after rinsing in 40 ℃ of vacuum, makes titanium alloy surface redox graphene laminated film.
Titanium alloy surface redox graphene laminated film to preparation is tested, and result is as follows:
Adopt multifunction electronic energy spectrometer (XPS) to analyze the chemical composition of composite membrane, high definition C1s peak shows on titanium alloy has assembled graphene oxide, and hydroxyl, epoxy group(ing) and carboxyl after reduction on graphene oxide have disappeared.With UMT-2MT type frictional testing machines record laminated film load be 0.1N and slip velocity while being 1Hz frictional coefficient be 0.16 left and right, and there is no the titanium alloy T i of composite membrane
6al
4v frictional coefficient is 0.45, can see that laminated film demonstrates good tribological property.
Embodiment 3
A preparation method for titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polished finish
6al
4v puts into the ultrasonic 45min of 70% aqueous isopropanol, the Ti here
6al
4v is available Ti also
6al
7nb or Ti
12mo
5ta substitutes, then rinses 3 times with ultrapure water, then slowly puts into piranha solution 20min, after taking-up, again the titanium alloy after processing is put into new piranha solution 5min, makes titanium alloy surface hydroxylation.
B. by after hydroxylated titanium alloy use washed with de-ionized water 3 times, putting into propyl trimethoxy silicane content is the aminosilane solution self-assembly Silan-based Thin Films of 2mmol/L, and the time is 2h.
C. graphene oxide powder is put into distilled water, ultrasonic wave is disperseed 30min, and obtaining concentration is the graphene oxide colloid that 0.1mg/mL is stable.
D. the titanium alloy immersion graphene oxide colloid with silane by surface keeps 60 ℃ of lasting 16h of constant temperature in encloses container, by the reaction of silane and graphene oxide, at titanium alloy surface, has just prepared silane-graphene composite thin film.
E. the titanium alloy with graphene oxide film is immersed to the mixing solutions (v/v=9:1) of 45%HBr and 30% phosphoric acid, heat 30min in encloses container, temperature is controlled at 100 ℃.By nucleophilic substitution reaction, the graphene oxide of titanium alloy surface is reduced.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing, for neutral, is then placed 24h by the product after rinsing in 40 ℃ of vacuum, makes titanium alloy surface redox graphene laminated film.
Embodiment 4
A preparation method for titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polished finish
6al
4v puts into the ultrasonic 45min of 70% isopropyl solution, the Ti here
6al
4v is available Ti also
6al
7nb or Ti
12mo
5ta substitutes, then rinses 3 times with ultrapure water, then slowly puts into piranha solution 20min, after taking-up, again the titanium alloy after processing is put into new piranha solution 5min, makes titanium alloy surface hydroxylation.
B. by after hydroxylated titanium alloy use washed with de-ionized water 3 times, putting into propyl trimethoxy silicane content is the aminosilane solution self-assembly Silan-based Thin Films of 1mmol/L, and the time is 2h.
C. graphene oxide powder is put into distilled water, ultrasonic wave is disperseed 30min, and obtaining concentration is the graphene oxide colloid that 1.0mg/mL is stable.
D. the titanium alloy immersion graphene oxide colloid with silane by surface keeps 60 ℃ of lasting 16h of constant temperature in encloses container, by the reaction of silane and graphene oxide, at titanium alloy surface, has just prepared silane-graphene composite thin film.
E. the titanium alloy with graphene oxide film is immersed to the mixing solutions (v/v=9:1) of 30%HI and 30% phosphoric acid, heat 30min in encloses container, temperature is controlled at 100 ℃.By nucleophilic substitution reaction, the graphene oxide of titanium alloy surface is reduced.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing, for neutral, is then placed 24h by the product after rinsing in 40 ℃ of vacuum, makes titanium alloy surface redox graphene laminated film.
Embodiment 5
A preparation method for titanium alloy surface graphene film, comprises the following steps:
A. by the titanium alloy T i of polished finish
6al
4v puts into the ultrasonic 45min of 70% isopropyl solution, the Ti here
6al
4v is available Ti also
6al
7nb or Ti
12mo
5ta substitutes, then rinses 3 times with ultrapure water, then slowly puts into piranha solution 20min, after taking-up, again the titanium alloy after processing is put into new piranha solution 5min, makes titanium alloy surface hydroxylation.
B. by after hydroxylated titanium alloy use washed with de-ionized water 3 times, putting into propyl trimethoxy silicane content is the aminosilane solution self-assembly Silan-based Thin Films of 1mmol/L, and the time is 2h.
C. graphene oxide powder is put into distilled water, ultrasonic wave is disperseed 30min, and obtaining concentration is the graphene oxide colloid that 1.0mg/mL is stable.
D. the titanium alloy immersion graphene oxide colloid with silane by surface keeps 60 ℃ of lasting 16h of constant temperature in encloses container, by the reaction of silane and graphene oxide, at titanium alloy surface, has just prepared silane-graphene composite thin film.
E. the titanium alloy with graphene oxide film is immersed to the mixing solutions (v/v=9:1) of 57%HI and 30% phosphoric acid, heat 30min in encloses container, temperature is controlled at 100 ℃.By nucleophilic substitution reaction, the graphene oxide of titanium alloy surface is reduced.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing, for neutral, is then placed 24h by the product after rinsing in 40 ℃ of vacuum, makes titanium alloy surface redox graphene laminated film.
Embodiment 6
A preparation method for titanium alloy surface graphene film, comprises the following steps:
Starting material used comprise: the graphene oxide powder that certain company produces.
A. by the titanium alloy T i of polished finish
6al
4v puts into the ultrasonic 45min of 70% isopropyl solution, the Ti here
6al
4v is available Ti also
6al
7nb or Ti
12mo
5ta substitutes, then rinses 3 times with ultrapure water, then slowly puts into piranha solution 20min, after taking-up, again the titanium alloy after processing is put into new piranha solution 5min, makes titanium alloy surface hydroxylation.
B. by after hydroxylated titanium alloy use washed with de-ionized water 3 times, putting into propyl trimethoxy silicane content is the aminosilane solution self-assembly Silan-based Thin Films of 1mmol/L, and the time is 2h.
C. graphene oxide powder is put into distilled water, ultrasonic wave is disperseed 30min, and obtaining concentration is the graphene oxide colloid that 1.0mg/mL is stable.
D. the titanium alloy immersion graphene oxide colloid with silane by surface keeps 60 ℃ of lasting 16h of constant temperature in encloses container, by the reaction of silane and graphene oxide, at titanium alloy surface, has just prepared silane-graphene composite thin film.
E. the titanium alloy with graphene oxide film is immersed to the mixing solutions (v/v=9:1) of 47%HBr and 30% phosphoric acid, heat 30min in encloses container, temperature is controlled at 100 ℃.By nucleophilic substitution reaction, the graphene oxide of titanium alloy surface is reduced.
F. the product with deionized water after reduction is rinsed repeatedly until the pH value of solution after rinsing, for neutral, is then placed 24h by the product after rinsing in 40 ℃ of vacuum, makes titanium alloy surface redox graphene laminated film.
Titanium alloy surface redox graphene laminated film to preparation is tested, and result is as follows:
Adopt multifunction electronic energy spectrometer (XPS) to analyze the chemical composition of composite membrane, high definition C1s peak shows on titanium alloy has assembled graphene oxide, and hydroxyl, epoxy group(ing) and carboxyl after reduction on graphene oxide have disappeared.With UMT-2MT type frictional testing machines record laminated film load be 0.1N and slip velocity while being 1Hz frictional coefficient be 0.14 left and right, and there is no the titanium alloy T i of composite membrane
6al
4v frictional coefficient is 0.45, illustrates that redox graphene laminated film has successfully been assembled in titanium alloy surface, and film has outstanding tribological property and good interface binding power, and the tribological property of titanium alloy significantly improves.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just can design according to the present invention make many modifications and variations without creative work.Therefore, all technician in the art, all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a preparation method for titanium alloy surface graphene film, is characterized in that, comprises the steps:
A. it is ultrasonic that the titanium alloy after surface finish being processed is put into aqueous isopropanol, with ultrapure water, rinse again, then slowly put into piranha solution standing, titanium alloy after standing processing is taken out and puts into new piranha solution again to carry out secondary standing, make titanium alloy surface hydroxylation;
B. by the titanium alloy after hydroxylation with after washed with de-ionized water, insert in aminosilane solution;
C. graphene oxide powder is put into distilled water, ultrasonic wave is disperseed, 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, in encloses container, continue to keep constant temperature;
E. the titanium alloy after described steps d is processed is immersed in the mixing solutions of haloid acid and phosphoric acid, in encloses container, heat;
F. by processing through described step e the product with deionized water obtaining, repeatedly rinse, until the pH value of solution after rinsing is neutral, then by the product drying after rinsing.
2. a preparation method for titanium alloy surface graphene film according to claim 1, is characterized in that, in described step a: described titanium alloy is selected from Ti
6al
4v, Ti
6al
7nb and Ti
12mo
5a kind of in Ta; The concentration of described Virahol is by mass percentage 70%; Described piranha solution is the vitriol oil that concentration is 98% by mass percentage and the hydrogen peroxide solution that 7:3 mixes by volume that concentration is 30% by mass percentage.
3. a preparation method for titanium alloy surface graphene film according to claim 2, is characterized in that, in described step a: described titanium alloy ultrasonic time in aqueous isopropanol is 30～60min; With ultrapure water washing time, it 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 characterized in that, in described step b, described aminosilane solution is that take by toluene and the water of the mixing of 5:1 volume ratio is solvent, with γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is solute, and the concentration of solute is 0.5～2mmol/L.
5. a preparation method for titanium alloy surface graphene film according to claim 4, is characterized in that, in described step b, with the number of times of washed with de-ionized water, is 3～5 times; The storing time of titanium alloy after hydroxylation in aminosilane solution solution is 2～12h.
6. a preparation method for titanium alloy surface graphene film according to claim 1, is characterized in that: the ultrasonic wave jitter time in described step c is 30min～2h; The concentration of the described graphene oxide colloid obtaining is 0.1～2mg/ml.
7. a preparation method for titanium alloy surface graphene film according to claim 1, is characterized in that: in described steps d, the steady temperature scope of described encloses container is that 40～80 ℃, constant temperature time length are 10～24h.
8. the preparation method of a titanium alloy surface graphene film according to claim 1, it is characterized in that: in described step e, described haloid acid is the HI solution that concentration is 30%～57% by mass percentage or the HBr solution that concentration is 30%～47% by mass percentage, and mixing solutions refers to the solution that described haloid acid and the phosphoric acid that concentration is 30% by mass percentage mix by 9:1 volume ratio.
9. a preparation method for titanium alloy surface graphene film according to claim 8, is characterized in that: in described step e, the time of the heating of titanium alloy in encloses container is 20min～10h, and heating and temperature control is at 40～100 ℃; Described dry finger in described step f is placed 24h in 40 ℃ of vacuum.
10. the utilization graphene-containing film titanium alloy material that as described in any one in claim 1 to 9 prepared by method.
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