CN109112329A - A kind of graphene/magnesium alloy and preparation method thereof with excellent interfacial characteristics - Google Patents
A kind of graphene/magnesium alloy and preparation method thereof with excellent interfacial characteristics Download PDFInfo
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Abstract
A kind of graphene/magnesium alloy and preparation method thereof with excellent interfacial characteristics, preparation step is as follows: (1) mixture of magnesium hydroxide and graphene oxide is formed using magnesium chloride hexahydrate, sodium hydroxide and graphite oxide alkene reaction；(2) mixture is restored using sodium borohydride, high-temperature calcination obtains the graphene powder of magnesia coating；(3) using the graphene powder of magnesia coating and magnesium alloy powder as raw material, under protective atmosphere, by selective laser fusing preparation using magnesia as graphene/magnesium alloy of interface phase.The present invention is using magnesium alloy as matrix, graphene as reinforced phase, magnesia as interface phase, on the one hand magnesia forms nanoscale contact and diffusion bond interface between graphene, on the other hand lattice structure is total in conjunction with magnesium alloy substrate by half, serving as interface bridge makes to form good interface cohesion between graphene and magnesium alloy, it realizes graphene tight magnesium crystal grain, and then improves the mechanical property and degradation drag of magnesium alloy.
Description
Technical field
The invention belongs to bio-medical implantation material preparation technical field, in particular to a kind of stone with excellent interfacial characteristics
Black alkene/magnesium alloy and preparation method thereof.
Background technique
In recent years, Biological magnesium alloy just becomes orthopedic implanting material due to good biocompatibility and biological degradability
Research hotspot.The density and elasticity modulus of Biological magnesium alloy and the density and elasticity modulus of skeleton are close, can be effectively reduced
" stress masking " effect.Moreover, magnesium is the indispensable element for maintaining human life activity, many metabolic responses and physiology can be participated in
Process.However, Biological magnesium alloy is highly prone to corrode in human body environment since normal potential is low (- 2.37V), lead to them
Degradation rate much higher than Bone Defect Repari requirement, it is likely that before new bone grows up to just lose structural intergrity.Therefore, biological magnesium is improved
The corrosion resistance and mechanical stability of alloy are its problems for being used for degradable implantation material urgent need to resolve.
Graphene is one kind by sp2The two-dimensional material that hydbridized carbon atoms are constituted has good permeability resistance and chemistry lazy
Property, the intrusion of corrosive medium can be hindered, therefore have great potential in terms of improving Corrosion Behaviors of Magnesium Alloys drag；Furthermore graphene
Also there is unique mechanical and physicochemical property, also obtain numerous studies as mechanics reinforced phase in recent years；There is research table simultaneously
Bright, graphene can be osteoblast by regulative transcription factor differentiation of stem cells.It therefore, if can be by graphene and magnesium alloy
It is compound, it is expected to obtain the magnesium alloy graft with excellent degradation drag and mechanical performance.However, graphene enhancing magnesium alloy
Significant challenge is: the two adheres to inorganic carbon and the two distinct types of material of metal, and graphene large specific surface area, Van der Waals separately
Active force is strong, is easy to reunite in magnesium alloy substrate, these factors cause the interface cohesion between graphene and magnesium alloy poor, and
It is well known that the interfacial characteristics between reinforced phase and matrix play decisive influence to the performance of composite material.
Therefore, how to improve the interface binding characteristic between graphene and magnesium alloy, and then give full play to graphene and changing
The great potential of kind degradation drag and mechanical properties, is Biological magnesium alloy in the degradable widely applied pass in implantation material field
Key.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of with excellent interfacial characteristics
Graphene/magnesium alloy and preparation method thereof, graphene/magnesium alloy mechanical property and degradation drag, which have, to be greatly improved, and is
A kind of good Biological magnesium alloy.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of graphene/magnesium alloy with excellent interfacial characteristics using magnesium alloy as matrix, graphene is reinforced phase, oxygen
Change magnesium is interface phase, and on the one hand magnesia forms nanoscale contact and diffusion bond interface between graphene, on the other hand logical
In conjunction with magnesium alloy substrate, serve as interface bridge makes to form good interface knot between graphene and magnesium alloy more than half lattice structures altogether
It closes, realizes graphene tight magnesium crystal grain.
The present invention also provides graphene/magnesium alloy preparation method with excellent interfacial characteristics, including it is as follows
Step:
(1) it is dispersed in the solvents ratio in 1L deionized water by 1g graphene oxide powder, by graphene oxide powder
In deionized water into ultrasonic disperse, magnesium chloride hexahydrate stirring is then added, it is molten that sodium hydroxide is added dropwise into stirring acquired solution
Liquid, continues to stir, and mixture one is obtained after vacuum filter；
(2) solvents ratio remains unchanged, and in deionized water by the dispersion of gained mixture one, solvents are than being added boron
Sodium hydride is simultaneously kept the temperature, and is then washed simultaneously vacuum filter repeatedly with dehydrated alcohol and deionized water, is obtained mixture two；
(3) under protective atmosphere, resulting mixture two is calcined, obtains the graphene powder of magnesia coating；
(4) graphene powder and magnesium alloy powder coated gained magnesia is ultrasonic in dehydrated alcohol respectively in proportion
Two kinds of solution after ultrasonic disperse, are then mixed and stirred for by dispersion, after vacuum filter, dry, obtain mixed-powder；
(5) using gained mixed-powder as raw material, it is passed through inert protective gas, is melted by selective laser and prepares biological magnesium conjunction
Gold, i.e. graphene/magnesium alloy.
Preferably, in the step (1), graphene oxide powder ultrasonic disperse 1 hour in 1L deionized water is added six
Aqueous magnesium chloride stirs 4 hours at 80 DEG C, continues stirring 12 hours after sodium hydroxide solution is added dropwise；In the step (2), it will mix
It closes object one to be dispersed in 1L deionized water, sodium borohydride is added and keeps the temperature 6 hours at 80 DEG C；In the step (3), by mixture
Two calcine 2 hours at 600 DEG C；In the step (4), the graphene powder of magnesia coating and magnesium alloy powder are existed respectively
Two kinds of solution after ultrasonic disperse are then mixed and stirred for 1 hour, wherein coating oxygen by ultrasonic disperse 2 hours in dehydrated alcohol
The graphene mass fraction for changing magnesium is 2.5-3.5wt.%；In the step (5), under inert protective gas atmosphere, H is controlled2O and
O2Concentration be lower than 30ppm, prepare Biological magnesium alloy during, control sweep span be 0.05-0.15mm, powdering with a thickness of
0.05-0.15mm, laser power 60-90W, scanning speed 100-500mm/min, spot diameter are 40-100 μm.
Preferably, the graphene oxide, magnesium chloride hexahydrate, sodium hydroxide, sodium borohydride mass ratio be 1:20:8:
10。
Preferably, in the step (4), the content for coating the graphene powder of magnesia is 3.0wt.%, magnesium alloy powder
The content at end is 97.0wt.%,
Preferably, in the step (4), the magnesium alloy powder is AZ61 powder, and the partial size of the AZ61 powder is 50-
80μm。
Preferably, the piece diameter of the graphene oxide powder is 8-15 μm.
Preferably, in the step (5), laser power 70-85W；Scanning speed is 150-300mm/min；Hot spot is straight
Diameter is 65-85 μm；Sweep span is 0.08-0.13mm；Powdering is with a thickness of 0.07-0.13mm.
It is highly preferred that in the step (5), laser power 80W；Scanning speed is 200mm/min；Spot diameter is 80
μm；Sweep span is 0.1mm；Powdering is with a thickness of 0.1mm.
The principle of the present invention and beneficial effect compared with prior art are:
The present invention for the first time using magnesia coating graphene powder and magnesium alloy powder as raw material, using SLM technique at
Function is prepared for the magnesium alloy integral material with excellent interfacial characteristics.Nanoscale contact is wherein formed between graphene and magnesia
With diffusion bond interface, and magnesia and magnesium-based body interface form half lattice structure altogether, to make between graphene and magnesium alloy
Form good interface cohesion.This not only may insure that matrix stress is effectively transferred to graphene, play enhancing magnesium alloy machine
The effect of tool performance, moreover it is possible to make the strong package magnesium alloy crystal grain of graphene, it is lazy using its excellent permeability resistance and chemistry
Property hinder body fluid corrode, thus achieve the purpose that improve Biological magnesium alloy degradation property.
The mixing of dusty material mostly uses blend technique at present, although simple process, graphene and magnesia
Between only form physics contact interface, and be also easy to produce graphene-structured destroy and reunite the problems such as.Other technologies, as surface changes
Property and powder metallurgy etc., it is also very limited for the improvement of interfacial characteristics.The present invention is applied magnesia by special process
It overlays on graphene, makes to form nanoscale contact and diffusion bond interface between the two.In comparison, coating processes of the invention
Be conducive to evenly dispersed between graphene and magnesia and contact, to realize abundant between the two and stronger interface knot
It closes, and then gives full play to its strengthening effect.If will be generated miscellaneous in addition, coating processes parameter is higher than the scope of the invention in the present invention
Matter phase deteriorates alloy property；If being lower than the scope of the invention, since the magnesia quantity of formation is few, to graphene and magnesium alloy it
Between interface cohesion improvement it is unobvious.
The present invention makes graphene in alloy crystalline substance by the quick preparation of distinctive SLM realization of process parameters Biological magnesium alloy
Grain is outer to be wrapped to form dense protective layer, this provides necessary condition to improve the degradation drag of Biological magnesium alloy.Meanwhile it is high
Heating with cooling rate can be realized the refinement of alloy grain and increasing for number of grain boundaries, be conducive to improve the mechanics of alloy with
Degradation property.Moreover, graphene-structured will not generate destruction under special process of the present invention, this is the reinforcing for giving full play to graphene
Effect has more favorable advantage.
The graphene oxide sheet diameter that the present invention uses may be implemented effectively to wrap up magnesium alloy crystal grain, be contacted by reducing
Crystal grain is refined with inhibition forming core, while corrosive medium being hindered to invade, improves magnesium alloy degradation property.Piece diameter is too small, will be unable to
Complete crystallite-cladded, the high conductivity of graphene and specific surface area can make it form strong galvanic corrosion with matrix；Piece diameter mistake
Greatly, graphene easily folds, and reduces interface cohesion effect.The graphene powder content of magnesia, energy are coated in the present invention
Enough interface cohesions for greatly improving graphene and magnesium alloy are compared using the graphene powder of higher amount coating magnesia
There is agglomeration in the magnesium alloy in experiment, discovery graphene, this will greatly weaken the interface fine structure even shape of the two
At hole, cause matrix stress that can not be effectively passed on graphene, reduces its mechanics strengthening effect, and hole can reduce graphite
The package protective effect of alkene, effectively cannot hinder corrosive medium to invade, to form strong galvanic corrosion with magnesium matrix, dislike
The degradation property of alloy is changed.
In conclusion the selection of each parameter is not random value in the present invention, but tested many times by inventor,
The crystallization made the creative labor, the present invention by raw material size, ratio control and it is distinctive coating and SLM technique,
Under the synergistic effect of various technological parameters, make to form nanoscale contact and diffusion bond circle between graphene and magnesia
Half is formd between face, magnesia and magnesium-based matter and is total to lattice structure, and then makes to form between graphene and magnesium alloy good
Interface cohesion realizes the raising of Biological magnesium alloy performance.
Detailed description of the invention
Fig. 1 is the XRD diagram of products therefrom under different coating parameters of the invention.
Fig. 2 is the Raman spectrogram before and after SLM technique.
Specific embodiment
The embodiment that the present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment 1
By 1 gram of graphene oxide powder in 1L deionized water ultrasonic disperse 1 hour, then be added 20 grams of magnesium chloride hexahydrates
And stirred 4 hours at 80 DEG C, then the sodium hydroxide solution that 1L concentration is 0.2mol/L is slowly added dropwise into solution, continue to stir
12 hours, mixture one is obtained after vacuum filter；Said mixture one is dispersed in 1L deionized water, 10 grams of boron hydrogen are added
Change sodium and keep the temperature 6 hours at 80 DEG C, then washs simultaneously vacuum filter repeatedly with dehydrated alcohol and deionized water, obtain mixture
Two；Under protective atmosphere, mixture two obtained above is calcined 2 hours at 600 DEG C, obtains the graphene of magnesia coating
Powder；The graphene mixed-powder and 9.7g AZ61 powder of 0.3g coating magnesia are weighed according to the mass ratio of 0.03:0.97
(purity > 99.9%, partial size~70 μm), ultrasonic disperse 2 hours in dehydrated alcohol respectively, then by two kinds after ultrasonic disperse
Solution is mixed and stirred for 1 hour, after vacuum filter, dry, obtains mixed-powder；Under protective atmosphere, in laser power
80W, scanning speed 200mm/min, 80 μm of spot diameter, sweep span 0.1mm, powdering thickness 0.1mm parameter under, utilize
SLM technique prepares Biological magnesium alloy.
Test discovery, magnesia successful application on graphene (Fig. 1), 3.0wt% coat the graphene uniform of magnesia
It is dispersed in alloy substrate, and forms good interface cohesion with magnesium alloy, graphene-structured does not have before and after laser action
Change (Fig. 2)；Yield strength is 242MPa, hardness 113HV；Corrosion potential is -1.40mVSCE, while it corrodes
Electric current is 0.2mm/y.These results indicate that magnesia is significantly improved by the interface cohesion of improvement magnesium alloy and graphene
The degradation drag and mechanical performance of Biological magnesium alloy.
Embodiment 2
By 1 gram of graphene oxide powder in 1L deionized water ultrasonic disperse 1 hour, then be added 20 grams of magnesium chloride hexahydrates
And stirred 4 hours at 80 DEG C, then the sodium hydroxide solution that 1L concentration is 0.2mol/L is slowly added dropwise into solution, continue to stir
12 hours, mixture one is obtained after vacuum filter；Said mixture one is dispersed in 1L deionized water, 10 grams of boron hydrogen are added
Change sodium and keep the temperature 6 hours at 80 DEG C, then washs simultaneously vacuum filter repeatedly with dehydrated alcohol and deionized water, obtain mixture
Two；Under protective atmosphere, mixture two obtained above is calcined 2 hours at 600 DEG C, obtains the graphene of magnesia coating
Powder；According to 0.03:0.975 mass ratio weigh 0.3g coating magnesia graphene powder and 9.7g AZ61 powder (degree >
99.9%, partial size~70 μm), the graphene powder and AZ61 powder that above-mentioned magnesia is coated are ultrasonic in dehydrated alcohol respectively
Two kinds of solution after ultrasonic disperse, are then mixed and stirred for 1 hour by dispersion 2 hours, after vacuum filter, dry, are mixed
Close powder；It is straight in laser power 80W, scanning speed 220mm/min, hot spot in the case where purity is the protection of 99.999% high-purity argon gas
80 μm of diameter, sweep span 0.9mm, powdering thickness 0.11mm parameter under, utilize SLM technique prepare Biological magnesium alloy.
The graphene uniform of test discovery, 2.5wt% coating magnesia is dispersed in AZ61 alloy substrate, and is closed with magnesium
Gold forms good interface cohesion；Yield strength is 235MPa, hardness 100HV, corrosion potential is -1.45mVSCE, rotten
Erosion rate is 0.24mm/y.
Embodiment 3
By 1 gram of graphene oxide powder in 1L deionized water ultrasonic disperse 1 hour, then be added 20 grams of magnesium chloride hexahydrates
And stirred 4 hours at 80 DEG C, then the sodium hydroxide solution that 1L concentration is 0.2mol/L is slowly added dropwise into solution, continue to stir
12 hours, mixture one is obtained after vacuum filter；Said mixture one is dispersed in 1L deionized water, 10 grams of boron hydrogen are added
Change sodium and keep the temperature 6 hours at 80 DEG C, then washs simultaneously vacuum filter repeatedly with dehydrated alcohol and deionized water, obtain mixture
Two；Under protective atmosphere, mixture two obtained above is calcined 2 hours at 600 DEG C, obtains the graphene of magnesia coating
Powder；According to 0.035:0.965 mass ratio weigh 0.35g coating magnesia graphene powder and 965gAZ61 powder (degree >
99.9%, partial size~70 μm), the graphene powder and AZ61 powder that above-mentioned magnesia is coated are ultrasonic in dehydrated alcohol respectively
Two kinds of solution after ultrasonic disperse, are then mixed and stirred for 1 hour by dispersion 2 hours, after vacuum filter, dry, are mixed
Close powder；It is straight in laser power 80W, scanning speed 200mm/min, hot spot in the case where purity is the protection of 99.999% high-purity argon gas
80 μm of diameter, sweep span 0.1mm, powdering prepare Biological magnesium alloy using SLM technique with a thickness of under the parameter of 0.1mm.
Test discovery, the graphene uniform of the coating magnesia of 3.5wt% is dispersed in AZ61 alloy substrate, and and magnesium
Alloy forms good interface cohesion；Yield strength is 220MPa, and hardness 101HV, corrosion potential is -1.50mVSCE, rotten
Erosion rate is 0.23mm/y.
In the technology of the present invention development process, have also been attempted following scheme (such as comparative example 1, comparative example 2, comparative example 3), but
The performance of products obtained therefrom is much worse than embodiment.
Comparative example 1
Other conditions are consistent with embodiment 1, the difference is that graphene oxide, magnesium chloride hexahydrate, sodium hydroxide, boron
The mass ratio of sodium hydride is 1:50:8:10, detects the performance of its products obtained therefrom, plurality of impurities occurs and be mutually distributed in grain boundary
(Fig. 1), is degrading the machinery and mechanical property of magnesium alloy, yield strength 195MPa, hardness 85HV, and corrosion potential is-
1.75mVSCE, corrosion rate 1.84mm/y.
Comparative example 2
Other conditions are consistent with embodiment, the difference is that, the graphene powder content for coating magnesia is 5%,
There are the graphene of reunion, yield strength 221MPa, hardness 99HV in test discovery products obtained therefrom, corrosion potential is-
1.62mVSCE, corrosion rate 0.5mm/y.
Comparative example 3
Other conditions are consistent with embodiment 1, the difference is that graphene film diameter is 4-7 μm, test discovery, graphene
Dispersed precipitate is on magnesium alloy grain boundary all in the form of the second phase, can not fully wrapped around firmly magnesium alloy since piece diameter is smaller
Crystal grain.Yield strength is 210MPa, and hardness 95HV, corrosion potential is -1.65mVSCE, corrosion rate 2.04mm/y.
Comparative example 4
Other conditions are consistent with embodiment, the difference is that, laser power 100W, test is found in products obtained therefrom
Graphene-structured changes (Fig. 2), yield strength 204MPa, hardness 85HV, and corrosion potential is -1.62mVSCE, corrosion
Rate is 1.05mm/y.
Claims (10)
1. a kind of graphene/magnesium alloy with excellent interfacial characteristics, which is characterized in that be by matrix, graphene of magnesium alloy
Reinforced phase, magnesia are interface phase, and on the one hand magnesia forms nanoscale contact and diffusion bond interface between graphene, separately
On the one hand by half, for lattice structure in conjunction with magnesium alloy substrate, serving as interface bridge keeps formation between graphene and magnesium alloy good altogether
Interface cohesion, realize graphene tight magnesium crystal grain.
2. with graphene/magnesium alloy preparation method of excellent interfacial characteristics described in claim 1, which is characterized in that including
Following steps:
(1) it is dispersed in the solvents ratio in 1L deionized water by 1g graphene oxide powder, graphene oxide powder is being gone
Into ultrasonic disperse in ionized water, magnesium chloride hexahydrate stirring is then added, sodium hydroxide solution is added dropwise into stirring acquired solution, after
Continuous stirring, obtains mixture one after vacuum filter；
(2) solvents ratio remains unchanged, and in deionized water by the dispersion of gained mixture one, sodium borohydride is added and keeps the temperature,
Simultaneously vacuum filter is then washed repeatedly with dehydrated alcohol and deionized water, obtains mixture two；
(3) under protective atmosphere, resulting mixture two is calcined, obtains the graphene powder of magnesia coating；
(4) graphene powder and magnesium alloy powder coated gained magnesia in proportion divide in dehydrated alcohol respectively by ultrasound
It dissipates, is then mixed and stirred for two kinds of solution after ultrasonic disperse, after vacuum filter, dry, obtain mixed-powder；
(5) using gained mixed-powder as raw material, it is passed through inert protective gas, preparation Biological magnesium alloy is melted by selective laser,
That is graphene/magnesium alloy.
3. according to claim 2 with graphene/magnesium alloy preparation method of excellent interfacial characteristics, which is characterized in that
In the step (1), magnesium chloride hexahydrate is added at 80 DEG C in graphene oxide powder ultrasonic disperse 1 hour in deionized water
Stirring 4 hours continues stirring 12 hours after sodium hydroxide solution is added dropwise；In the step (2), mixture one is dispersed in 1L
In ionized water, sodium borohydride is added and keeps the temperature 6 hours at 80 DEG C；In the step (3), mixture two is calcined 2 at 600 DEG C
Hour；In the step (4), the graphene powder and magnesium alloy powder that magnesia is coated respectively divide in dehydrated alcohol by ultrasound
It dissipates 2 hours, is then mixed and stirred for two kinds of solution after ultrasonic disperse 1 hour, wherein the graphene quality of coating magnesia
Score is 2.5-3.5wt.%；In the step (5), under inert protective gas atmosphere, H is controlled2O and O2Concentration is lower than 30ppm,
During preparing Biological magnesium alloy, control sweep span is 0.05-0.15mm, and powdering is with a thickness of 0.05-0.15mm, laser power
For 60-90W, scanning speed 100-500mm/min, spot diameter is 40-100 μm.
4. having graphene/magnesium alloy preparation method of excellent interfacial characteristics according to Claims 2 or 3, feature exists
In the mass ratio of, the graphene oxide, magnesium chloride hexahydrate, sodium hydroxide, sodium borohydride be 1:20:8:10.
5. having graphene/magnesium alloy preparation method of excellent interfacial characteristics according to Claims 2 or 3, feature exists
In in the step (4), the content for coating the graphene powder of magnesia is 3.0wt.%, and the content of magnesium alloy powder is
97.0wt.%.
6. having graphene/magnesium alloy preparation method of excellent interfacial characteristics according to Claims 2 or 3, feature exists
In in the step (4), the magnesium alloy powder is AZ61 powder.
7. according to claim 6 with graphene/magnesium alloy preparation method of excellent interfacial characteristics, which is characterized in that
The partial size of the AZ61 powder is 50-80 μm.
8. according to claim 2 with graphene/magnesium alloy preparation method of excellent interfacial characteristics, which is characterized in that
The piece diameter of the graphene oxide powder is 8-15 μm.
9. according to claim 2 with graphene/magnesium alloy preparation method of excellent interfacial characteristics, which is characterized in that
In the step (5), laser power 70-85W；Scanning speed is 150-300mm/min；Spot diameter is 65-85 μm；Scanning
Spacing is 0.08-0.13mm；Powdering is with a thickness of 0.07-0.13mm.
10. according to claim 2 with graphene/magnesium alloy preparation method of excellent interfacial characteristics, which is characterized in that
In the step (5), laser power 80W；Scanning speed is 200mm/min；Spot diameter is 80 μm；Sweep span is
0.1mm；Powdering is with a thickness of 0.1mm.
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