CN110184564A - The preparation method of Mg alloy surface low stress, high bond strength Si/DLC thick film - Google Patents
The preparation method of Mg alloy surface low stress, high bond strength Si/DLC thick film Download PDFInfo
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- CN110184564A CN110184564A CN201910587317.2A CN201910587317A CN110184564A CN 110184564 A CN110184564 A CN 110184564A CN 201910587317 A CN201910587317 A CN 201910587317A CN 110184564 A CN110184564 A CN 110184564A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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Abstract
The preparation method of Mg alloy surface low stress, high bond strength Si/DLC thick film is related to the preparation method of a kind of nanometer of period Si/DLC thick film.Method: the one, pre-treatment of magnesium alloy substrate；Two, prepare before plated film；Three, Si transition buffer layer is prepared；Four, DLC hard layer is prepared；Five, the alternate nanometer period thick film of Si/DLC is prepared, the higher high-quality Si/DLC thick film of film-substrate cohesion is obtained.This method is by DC power supply, grid bias power supply and copper coil connected applications in magnetron sputtering technique, this method is simple, it is the advanced method of a kind of low stress, the preparation of high bond strength thick film, aura is continual and steady in magnetron sputtering process, the thick film dense uniform of preparation, film substrate bond strength is high, eliminate columnar crystal structure in traditional PVD method, while improving hardness, corrosive nature is improved again, this reduces abrasion, economize on resources important in inhibiting and prospect for the raising of Mg alloy surface performance and the application of expansion magnesium alloy.
Description
Technical field
The present invention relates to the preparation method of a kind of nanometer of period Si/DLC thick film, fields are that surface treatment and material are protected
Shield.
Background technique
Resource consumption is the major issue that current human kind sustainable development is faced.Magnesium alloy density is small, can effectively mitigate
The weight of the vehicles such as aircraft, automobile, energy-saving and emission-reduction, protection environment.And magnesium alloy has preferable electromagnetic wave shielding, resists
Shake noise abatement performance and machinability, higher specific strength and specific stiffness, elasticity modulus and skeleton and cortical bone tissue
It is close, there is good biocompatibility, nontoxic, this makes magnesium alloy in communications and transportation, aerospace, 3C Product, militarization
The fields such as work and biomedicine use on a large scale.However, magnesium alloy chemical property is active, it can be raw with air reaction under room temperature
At loose MgO, there is no protective effect to matrix.And magnesium alloy hardness is lower, and it is not wear-resisting.Corrosion and the big factor limit of abrasion two
The application and popularization for having made magnesium alloy, cause huge economic loss.Surface coating technology can solve the above problem, and protect
Under the premise of demonstrate,proving substrate performance, and improve substrate performance.But tradition thicknesses of layers is limited, generally below 5 μm, this is for mentioning
The limited extent of high-wear resistance.DLC thick film, the lubrication of C element and the guarantee of thickness can solve magnesium alloy and apply in abrasion
In trouble and worry, and DLC amorphous structure eliminates column crystal, reduces corrosive ion by film and enters matrix
Channel, this is also a big benefit for the raising of corrosion resistance.
Summary of the invention
The present invention is to solve existing superficial hardness of magnesium alloy is lower, not wear-resisting, perishable problem provides a kind of magnesium and closes
The preparation method of gold surface low stress, high bond strength thick film.
The preparation method of Mg alloy surface low stress of the present invention, high bond strength Si/DLC thick film, comprising the following steps:
One, the pre-treatment of magnesium alloy substrate: magnesium alloy substrate is polished by abrasive paper for metallograph, NaOH aqueous slkali ultrasound is deoiled
Afterwards, pickling neutralizes, and with polishing after the washing of deionized water twice, then distinguishes ultrasonic in acetone, absolute ethanol and deionized water
Cleaning；
Two, prepare before plated film: matrix is in N2Cold wind dries up under gas, is put into magnetron sputtering vacuum chamber, vacuum chamber.
It is passed through Ar and regulates air pressure, under the collective effect of radio-frequency power supply and grid bias power supply, magnesium alloy substrate is banged using argon ion
It hits and carries out sputter clean and ion etching, and pre-sputtering is carried out to carbon target material under direct current+three kinds of bias+radio frequency power supply；
Three, prepare Si transition buffer layer: the tetramethylsilane that water-bath is evaporated is passed through vacuum chamber, and controls stream
Amount guides Si atom in silane into matrix under substrate negative voltage+direct current+coil effect, it is slow to obtain certain thickness Si transition
Layer is rushed, stress is not only discharged, improves film/film-substrate binding strength, and connection well is played for subsequent DLC film deposition and is made
With；
Four, it prepares DLC hard layer: being passed through argon gas, on the basis of Si transition buffer layer, using DC+ bias+coil mixing
Magnetically controlled sputter method deposits DLC hard layer by sputtering carbon target, obtains DLC hard layer-Si transition zone-substrate composite wood
Material；
Five, Si/DLC nanometers of period thick films are prepared: on DLC hard layer, tetramethylsilane that water-bath is evaporated
It is passed through vacuum chamber, regulates flow, continues to prepare certain thickness Si transition under the effect of substrate negative voltage+direct current+coil slow
Rush layer.Then on Si transition buffer layer, using DC+ bias+coil mixing magnetically controlled sputter method, continued by sputtering carbon target
DLC hard layer is deposited, goes down repeatedly, obtains the composite material of DLC/Si-DLC/Si-DLC/Si......- substrate.
Further, substrate pretreatment method described in step 1: matrix successively use 280#, 500#, 800#, 1000#,
The abrasive paper for metallograph of 1500# and 2000# is polished, and is cleaned by ultrasonic 10min~30min after polishing in NaOH solution, then neutralized with acid,
Deionized water twice polish after rinsing, and the matrix after polishing cleans 10 in the ultra sonic bath of acetone, dehydrated alcohol and DI water respectively
~30min, 150~200W of ultrasonic power.
Further, concrete operations in the preparation and power configuration before plated film described in step 2 are as follows: after ultrasonic cleaning
Matrix is in N2Cold wind dries up under gas, is put into magnetron sputtering vacuum chamber, vacuum chamber, background vacuum 5 × 10-4~3 ×
10-3Pa.Be passed through Ar and regulate 0.5~1.5Pa of air pressure, Ar flow be 15~30sccm, radio-frequency power supply (power be 160~
280W) and grid bias power supply (- 500V~-1500V) collective effect under sputter clean and etch 15~30min of substrate obtain it is pure
Matrix.Carbon target pre-sputtering parameter are as follows: DC current is 0.3~1.0A, and substrate bias is -500~-1500V, radio-frequency power supply power
For 160~280W, coil current is 5~15A, 50~150 circle of the number of turns, operating air pressure 0.5~1.5Pa, Ar flow is 15~
30sccm, 10~20min of pre-sputtering time, obtains pure target.
Further, the concrete operations of the excessive buffer layer of Si are prepared described in step 3 are as follows: first by cleaned matrix
Be fixed on specimen holder, open the traffic channel of tetramethylsilane, control 3~15sccm of flow, direct current (0.3~1.0A)+
Under coil (50~150 circles, 5~15A of coil current)+bias (- 200~-1000V) collective effect, sink on magnesium alloy substrate
Product Si transition buffer layer, buffer layer thickness are 0.3~1.0 μm, 0.5~1.5Pa of operating air pressure, 5~15min of sedimentation time.
Further, the concrete operations of DLC hard layer are prepared described in step 4 are as follows: be passed through sputter gas Ar (purity
99.00~99.999%), in direct current (0.3~1.0A)+bias (- 200~-1000V)+coil (50~150 circles, coil current
5~15A) hard DLC layer, target and matrix distance 60~100mm, Ar flow are prepared by sputtering carbon target under three's immixture
For 15~30sccm, 0.5~1.5Pa of operating air pressure, 10~20min of sputtering time, hard layer is with a thickness of 0.5~1.5 μm.
Further, the concrete operations of the alternate nanometer period thick film of Si/DLC are prepared described in step 5 are as follows: be passed through again
Tetramethylsilane controls 3~15sccm of flow into vacuum chamber, according to described in step 3 in direct current (0.3~1.0A)+coil
Under (50~150 circles, 5~15A of coil current)+bias (- 200~-1000V) collective effect, sink again on magnesium alloy substrate
Product Si transition buffer layer, buffer layer thickness are 0.3~1.0 μm, 0.5~1.5Pa of operating air pressure, 5~15min of sedimentation time.And
Afterwards close tetramethylsilane gas circuit, be passed through argon gas, according to step 4 require direct current (0.3~1.0A)+bias (- 200~-
It is hard that the lower continuation of 1000V)+coil (50~150 circles, 5~15A of coil current) three effect prepares DLC on Si transition buffer layer
Matter layer, Ar flow be 15~30sccm, 0.5~1.5Pa of operating air pressure, 10~20min of sputtering time, 0.5~1.5 μm of thickness.
Go down repeatedly, obtains the alternate nanometer period thick film of Si/DLC, 20~40 layers of total number of plies of period thick film, overall thickness 30~
50μm。
Beneficial effects of the present invention:
1, the present invention is to prepare Si/DLC nanometers in Mg alloy surface using direct current+bias+coil magnetron sputtering technique
Period thick film the characteristics of using tetramethylsilane low boiling point, makes it into vacuum chamber by volatilization, Si atom is provided, in direct current
Under effect, deposition is high, is biased and film-substrate cohesion can be improved.Additional coil increases the magnetic field at the cathode carbon target back side
Intensity improves film quality and productivity.
2, it is prepared by the alternating of Si transition zone, is entrained among DLC hard layer, oxygen atom not only can be absorbed, improved
Film-substrate cohesion, and greatly reduce thick film residual stress is verified by the ψ scan pattern of X-ray diffraction, using Si as delaying
The Si/DLC thick film residual compressive stress for rushing layer is 719.42 ± 11.25MPa, is lower than pure DLC thick film residual stress, also below other
The stress of the DLC thick film of certain methods preparation.It is monitored by the acoustic emission signal of coating adhesion scratching instrument, it is known that in the present invention
The film-substrate cohesion of Si/DLC thick film is greater than 46N.Therefore Si/DLC thick film prepared by the present invention has low stress, the high property combined
Energy；
3, Si/DLC period thick film in the present invention learns that membrane structure is nanocrystalline and amorphous carbon through HRTEM observation
Mixed structure eliminates columnar crystal structure in traditional PVD method, reduces the channel of extraneous corrosive ion intrusion matrix.And
And it is nanocrystalline tiny, amorphous carbon has good lubricant effect.Therefore, such structure is conducive to improve the anti-corrosion of film and resistance to
Grind performance；
4, the method for the present invention is safe and reliable, green non-pollution, high production efficiency, at low cost, equipment are simple and convenient to operate,
It is worthy to be popularized.
The method of the present invention is by direct current, bias and coil connected applications in magnetron sputtering technique, and three acts synergistically, mutually
Learn from other's strong points to offset one's weaknesses, promotes mutually, magnetron sputtering is continual and steady, and the thick film stress of preparation is lower, bond strength is higher.
Detailed description of the invention
Fig. 1 is the schematic diagram of a layer structure of Si/DLC period thick film prepared by embodiment 1；
Fig. 2 is Si/DLC period thick film X-ray ψ scan pattern schematic diagram prepared by embodiment 1.ψ is sample surfaces in figure
Angle between normal direction and measurement normal of crystal surface direction, k0 and k are respectively the wave vector of incident X-rays and diffracting X-rays, and P is sample
Product surface normal direction, S3 are measurement normal of crystal surface direction, and θ is the Bragg angle for measuring crystal face；
Fig. 3 is the residual stress curve for the Si/DLC period thick film that X-ray ψ scanning fits in embodiment 1；
Fig. 4 is the sound emission curve of Si/DLC period thick film in embodiment 1；
Fig. 5 is the HRTEM observed result of Si/DLC period thick film in embodiment 1；
Fig. 6 is the electrochemical tests of Si/DLC period thick film in embodiment 1；
Fig. 7 is the friction coefficient curve of the Si/DLC period thick film prepared in embodiment 1.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: the preparation of present embodiment Mg alloy surface low stress, high bond strength Si/DLC thick film
Method, comprising the following steps:
One, the pre-treatment of magnesium alloy substrate: magnesium alloy substrate is polished by abrasive paper for metallograph, after alkali cleaning is deoiled and is polished,
It is cleaned by ultrasonic in acetone, absolute ethanol and deionized water respectively；
Two, prepare before plated film: the matrix after step 1 is cleaned is in N2Cold wind drying is put into the true of magnetron sputtering under air-flow
It in empty room, vacuumizes, is lower than 1 × 10 to vacuum degree-3It after Pa, is passed through argon gas and adjusts vacuum room pressure, open radio-frequency power supply
And grid bias power supply, sputter clean simultaneously etches 15~30min of magnesium alloy substrate, then to carbon target under direct current+bias+radio frequency conditions
Carry out pre-sputtering；
Three, it prepares Si transition buffer layer: using direct current+coil+bias mixed method, water-bath being volatized into vacuum
The tetramethylsilane of room is deposited on matrix, prepares Si transition buffer layer；
Four, it prepares DLC hard layer: being passed through argon gas, on Si transition buffer layer, using direct current+bias+coil mixing magnetic
Sputtering method is controlled, DLC hard layer is deposited by sputtering carbon target；
Five, Si/DLC nanometers of period thick films are prepared: according to the method for step 3, using direct current+bias+coil mixing side
Method continues to deposit Si transition buffer layer on the DLC hard layer that the 4th step prepares.Then redeposited according to the method for step 4
DLC hard layer is prepared, is so continued, the alternate nanometer period thick film of Si/DLC is prepared.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: magnesium alloy base described in step 1
The constituent content of body are as follows: Al:3.0911wt.%, Zn:0.7862wt.%, Mn:0.2863wt.%, Mg: surplus.Other and tool
Body embodiment one is identical.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: it is beaten described in step 1
Mill is successively polished using the abrasive paper for metallograph of 280#, 500#, 800#, 1000#, 1500# and 2000#.Other and specific embodiment
One or two is identical.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: institute in step 1
State polishing are as follows: the matrix after air exercise mill is in Al2O3Polishing treatment under the action of antiscuffing paste.Other and specific embodiment one to three
One of it is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: institute in step 1
The time for stating ultrasonic cleaning is 10~30min, and ultrasonic power is 150~200W.One of other and specific embodiment one to four
It is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: being penetrated in step 2
Frequency power power is 160~280W, rf frequency 13.56MHz.It is other identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: in step 2 partially
Voltage source voltage is -500V~-1500V.It is other identical as one of specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: target in step 2
Material pre-sputtering parameter are as follows: DC current is 0.3~1.0A, and radio-frequency power is 160~280W, rf frequency 13.56MHz, base
Body-bias be -500~-1500V, operating air pressure 0.5~1.5Pa, Ar flow be 15~30sccm, the pre-sputtering time 10~
20min.It is other identical as one of specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: institute in step 3
That states prepares the concrete operations of the excessive buffer layer of Si are as follows: cleaned matrix is fixed on specimen holder first, opens flow valve
Switch, set 3~15sccm of tetramethylsilane flow, direct current (0.3~1.0A)+coil (50~150 circles, coil current 5~
Under 15A)+bias (- 200~-1000V) collective effect, Si transition buffer layer, operating air pressure 0.5 are deposited on magnesium alloy substrate
~1.5Pa.It is other identical as one of specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: Si in step 3
Transition buffer layer with a thickness of 0.3~1.0 μm, 5~15min of sedimentation time.Other phases one of with specific embodiment one to nine
Together.
Specific embodiment 11: unlike one of present embodiment and specific embodiment one to ten: in step 4
The concrete operations of the magnetically controlled sputter method of the direct current+bias+coil mixing are as follows: be passed through sputter gas Ar (purity 99.00~
99.999%), DC current be 0.3~1.0A, bias be -200~-1000V, 50~150 circle of coil, coil current be 5~
15A, three kinds of power supply effects are lower to prepare hard DLC layer, target and 60~100mm of matrix distance by sputtering carbon target, and Ar flow is
15~30sccm, 10~20min of sputtering time, 0.5~1.5Pa of operating air pressure.One of other and specific embodiment one to ten
It is identical.
Specific embodiment 12: present embodiment is unlike specific embodiment one to one of 11: step 4
Middle DLC hard layer with a thickness of 0.5~1.5 μm.It is other identical as specific embodiment one to one of 11.
Specific embodiment 13: present embodiment is unlike specific embodiment one to one of 12: step 5
Described in prepare the concrete operations of Si/DLC nanometers of period thick films are as follows: be passed through tetramethylsilane, 3~15sccm of flow, straight again
It flows under (0.3~1.0A)+coil (50~150 circles, 5~15A of coil current)+bias (- 200~-1000V) collective effect,
Si transition buffer layer is deposited on magnesium alloy substrate again, 0.5~1.0Pa of operating air pressure deposits 5~15min.Then in direct current
Continue to make under (0.3~1.0A)+bias (- 200~-1000V)+coil (50~150 circles, 5~15A of coil current) three effect
Standby DLC hard layer, Ar flow are 15~30sccm, 0.5~1.5Pa of operating air pressure, 10~20min of sputtering time.Repeatedly
Go down, obtains the alternate nanometer period thick film of Si/DLC.It is other identical as specific embodiment one to one of 12.
Specific embodiment 14: present embodiment is unlike specific embodiment one to one of 13: step 5
20~40 layers of total number of plies of middle Si/DLC nanometers of period thick film, 30~50 μm of overall thickness.Other and specific embodiment one to ten
One of three is identical.
Elaborate below to the embodiment of the present invention, following embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1:
The preparation method of the present embodiment Mg alloy surface low stress, high bond strength Si/DLC thick film
The following steps are included:
One, the pre-treatment of magnesium alloy substrate: abrasive paper for metallograph will be carried out having a size of 20mm × 20mm × 3mm magnesium alloy substrate
Polish step by step, be cleaned by ultrasonic in NaOH aqueous slkali and deoil, in pickling and remaining lye and with after the flushing of deionized water twice
Al2O3It is polished under the action of antiscuffing paste, obtains the matrix of any surface finish.Then matrix in acetone, dehydrated alcohol and is gone respectively again
It is cleaned by ultrasonic in ionized water, the time of ultrasonic cleaning is 20min.The wherein constituent content of described matrix are as follows: Al:
3.0911wt.%, Zn:0.7862wt.%, Mn:0.2863wt.%, Mg: surplus.It is described polishing successively using 280#, 500#,
The abrasive paper for metallograph of 800#, 1000#, 1500# and 2000# are polished.
Two, the preparation before plated film: in N2Cold wind drying is put into the vacuum chamber of magnetron sputtering under air-flow.Carbon target is installed
It is good, the substrate cleaned is fixed on specimen holder, adjusts target at a distance from specimen holder, vacuum chamber top cover is then closed and examines
Look into the air-tightness of vacuum chamber.Wound around coil on the outside of target, for enhancing magnetic field strength.Later on mechanical pump vacuumizes, surely
When reciprocal of duty cycle is lower than 10Pa, opens molecular pump and further vacuumize, until indoor background vacuum≤1 × 10 of vacuum-3Pa.It is passed through
Argon gas simultaneously adjusts vacuum room pressure, then opens radio-frequency power supply and grid bias power supply, sputter clean simultaneously etch magnesium alloy substrate, this
Sample can increase the binding performance of film and matrix.Then, in order to guarantee the cleaning of target material surface, impurity is avoided to be deposited on matrix
Surface pollutes, and also to carry out pre-sputtering to carbon target under direct current+three kinds of bias+radio frequency power supply effect before plated film, open gear
Plate, the particle deposition for making pre-sputtering get off avoid pollution matrix on baffle.
Three, it prepares Si transition buffer layer: being passed through tetramethylsilane, existed using direct current+bias+coil magnetron sputtering technique
Matrix surface prepares Si transition buffer layer after ion etching cleaning, obtains Si transition buffer layer-matrix.
Four, it prepares DLC hard layer: being passed through argon gas, prepare DLC using direct current+bias+coil combined magnetic-controlled sputter technology
Hard layer obtains DLC hard layer-Si transition buffer layer-matrix.
Five, Si/DLC nanometers of period thick films are prepared: being passed through tetramethylsilane, it is composite magnetic controlled using direct current+bias+coil
Sputtering technology continues to deposit Si transition buffer layer on DLC hard layer, is then shut off the gas circuit of tetramethylsilane, is passed through argon gas,
Continue to deposit DLC hard layer on Si transition buffer layer, so continues, obtain DLC hard layer-Si and excessively buffer
Layer-... .- matrix completes the preparation in Si/DLC nanometers of period thick films of magnesium alloy matrix surface.
Ultrasonic power described in step 1 is 200W.
Radio-frequency power supply power described in step 2 is 160W, rf frequency 13.56MHz；Bias mains voltage is -500V.
Target pre-sputtering parameter in step 2 are as follows: DC current 0.6A, substrate bias are -500V, operating air pressure
1.0Pa, Ar flow are 25sccm, pre-sputtering time 20min.
Direct current described in step 3+bias+coil magnetron sputtering technique concrete operations are as follows: vacuum chamber is passed through tetramethyl
Silane, flow 8sccm, under direct current (0.6A)+bias (- 500V)+coil (100 circles, coil current 10A) collective effect,
Si transition buffer layer, buffer layer thickness 500nm, operating air pressure 1.0Pa, sedimentation time 10min are constructed on magnesium alloy substrate.
Using the concrete operations of direct current+bias+coil combined magnetic-controlled sputter technology described in step 4 are as follows: be passed through sputtering
Gas Ar (purity 99.999%) makees jointly in direct current (0.6A)+bias (- 500V)+coil (100 circles, coil current 10A)
DLC hard layer is constructed on Si transition buffer layer under, Ar flow is 25sccm, operating air pressure 1.0Pa, sputtering time 15min.
The concrete operations of Si/DLC nanometers of period thick films are prepared described in step 5 are as follows: close argon gas, vacuum chamber is passed through four
Methyl-monosilane, flow 8sccm, under direct current (0.6A)+bias (- 500V)+coil (100 circles, 10A) collective effect, just
Continue to deposit Si transition buffer layer, buffer layer thickness 500nm, operating air pressure 1.0Pa, deposition on the DLC hard layer of deposition
10min.Be then shut off the gas circuit of tetramethylsilane, vacuum chamber is passed through Ar gas (purity 99.999%), direct current (0.6A)+partially
DLC hard is deposited again on the Si transition buffer layer just prepared under pressure (- 500V)+coil (100 circles, 10A) collective effect
Layer, Ar flow are 25sccm, operating air pressure 1.0Pa, sputtering time 15min.It goes on repeatedly, finally obtains Si/DLC
Nanometer period thick film, Si and 36 layers, 48 μm of overall thickness of the total number of plies of DLC.
The schematic diagram of a layer structure for the Si/DLC thick film that the present embodiment step 5 obtains is as shown in Figure 1.
This method uses direct current+bias+coil complex technique, and preparation efficiency is high, economical and practical.Using Si as buffering
Transition zone solves the problems, such as that stress is larger and binding force is poor since thermal physical property parameter difference is brought between matrix and film, mentions
High film/base binding performance, and Si transition zone is applied in always among DLC hard layer, not only reduces the residual stress of thick film,
And good connection function is played between the layers.The amorphous structure of DLC film layer eliminates column in traditional PVD method
Crystal structure reduces the channel of extraneous corrosive ion intrusion matrix.Moreover, amorphous carbon has good lubricant effect again,
It is very helpful for the anti-corrosion and wear-resisting property that improve magnesium alloy substrate.
Using the residual stress of X-ray ψ scan method test Si/DLC thick film, X-ray ψ scanning is as shown in Figure 2.Fig. 3 is ψ
The residual-stress value that scan method obtains is as can be seen from Figure 3 that (this is to inhibition film underbead crack for residual compressive stress inside film
Extension it is highly beneficial), numerical value be 719.42 ± 11.25MPa, for the thick film with a thickness of 48 μm, it is known that prepared
Si/DLC nanometers of period membrane stresses are lower.
Fig. 4 is the HRTEM observed result of Si/DLC thick film.F20 type transmission electron microscope observation result learns, this method
The film layer structure obtained using direct current+bias+coil magnetron sputtering technique are as follows: the tiny Si Nanocrystals Embedded of size is amorphous
On carbon, this structure proves that Si/DLC thick film manufactured in the present embodiment is quality material.
Fig. 5 is the curve that coating adhesion acoustic emission test goes out.As shown in Figure 5, the Si/DLC of the method for the present invention preparation is thick
The film-substrate cohesion of film is greater than 46N, and for 48 μm of thick film, bond strength is higher.
Fig. 6 is the electrochemical corrosion test polarization curve of Si/DLC thick film.It will be appreciated from fig. 6 that the Si/ of the method for the present invention preparation
The corrosion potential of DLC thick film is -0.957V, corrosion electric current density 1.82 × 10-6A/cm2, it was demonstrated that Si/DLC thick film it is corrosion-resistant
Better performances.
Fig. 7 is the friction coefficient curve of Si/DLC thick film.As shown in Figure 7, the coefficient of friction of Si/DLC thick film is smaller, numerical value
0.11, show good wear-resisting property.
By above-mentioned experimental verification it is found that the present invention is a kind of side for preferably preparing low stress, high bond strength thick film
Method.
Not limited to this, any change or replacement expected without creative work should all be covered in guarantor of the invention
Within the scope of shield.Therefore, protection scope of the present invention should be determined by the scope of protection defined in the claims.
Claims (10)
1. the preparation method of Mg alloy surface low stress, high bond strength Si/DLC thick film, it is characterised in that this method include with
Lower step:
One, it the pre-treatment of magnesium alloy substrate: after magnesium alloy substrate wire cutting sampling, polishes by different meshes abrasive paper for metallograph
Afterwards, it is cleaned by ultrasonic in NaOH aqueous slkali and degreases, pickling is washed and polished with deionized water twice after neutralizing, after polishing
Matrix is cleaned by ultrasonic in acetone, absolute ethanol and deionized water respectively；
Two, prepare before plated film: the matrix after step 1 is cleaned is in N2Cold wind drying is put into the vacuum chamber of magnetron sputtering under air-flow
It is interior, it checks vacuum chamber air-tightness, opens mechanical pump and molecular pump vacuumizes, be lower than 1 × 10 to vacuum degree in vacuum chamber-3Pa leads to
Enter argon gas and adjust vacuum room pressure, opens radio-frequency power supply and grid bias power supply, sputter clean simultaneously etch magnesium alloy substrate, then
Pre-sputtering is carried out to target using direct current+bias+radio frequency, when sputtering covers matrix with baffle；
Three, it prepares Si transition buffer layer: using tetramethylsilane low boiling point, volatile feature, it being heated in water-bath
Volatilization, provides Si atom, and the Si atom evaporated is deposited on magnesium alloy substrate under bias+direct current+coil power effect
Prepare Si transition buffer layer；
Four, it prepares DLC hard layer: being passed through argon gas, on Si transition buffer layer, splashed using direct current+bias+coil mixing magnetic control
Shooting method deposits preparation DLC hard layer by sputtering carbon target；
Five, Si/DLC nanometers of period thick films are prepared: being continued according to step 3 method in bias+direct current+coil on DLC hard layer
Under power supply, is volatilized by tetramethylsilane and prepare Si transition zone；Continue to prepare DLC hard according to step 4 on Si transition zone
Layer prepares Si/DLC nanometers of period thick films repeatedly.
2. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
Sign is that matrix described in step 1 can be AZ31, ZK60 or WE43.
3. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
Sign is that step 1 is respectively cleaned by ultrasonic 10~30min in NaOH, acetone, dehydrated alcohol, deionized water.
4. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
The gas pressure in vacuum that sign is that Ar ion pair substrate carries out ion etching cleaning in step 2 is 0.5Pa~1.5Pa, substrate bias
For -500V~-1500V, radio-frequency power supply power 160~280W, Ar flow is 15~30sccm, and 15min is cleaned in Ar ion etching
~30min obtains the magnesium alloy substrate of surface cleaning.
5. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
Sign is target pre-sputtering parameter in step 2 are as follows: DC current is 0.3~1.0A, and substrate bias is -500~-1500V, is penetrated
Frequency 160~280W of power, operating air pressure 0.5~1.5Pa, Ar flow are 15~30sccm, 10~20min of pre-sputtering time.
6. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
Sign is in step 3 that tetramethylsilane water bath temperature is 30~50 DEG C, and bias mains voltage is -200V~-1000V, direct current
0.3~1.0A of electric current, 5~15A of coil current, 50~150 circle of coil turn, 10~20min of sputtering time.
7. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
Sign be Si transition buffer layer in step 3 with a thickness of 0.3~1.0 μm, 5~15min of sedimentation time.
8. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
Sign is in step 4 that DC current is 0.3~1.0A, substrate bias -200~-1000V, 5~15A of coil current, coil turn
Number 50~150, matrix and target distance 60~100cm, Ar flow are 15~30sccm, 0.5~1.5Pa of operating air pressure, sputtering
10~20min of time, 0.5~1.5 μm of hard layer thickness.
9. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film, special
Sign be DLC hard layer in step 4 with a thickness of 0.5~2 μm.
10. the preparation method of Mg alloy surface low stress according to claim 1, high bond strength Si/DLC thick film,
It is characterized in that in step 5 that the total number of plies of Si and DLC is 20~40 layers, 30~50 μm of overall thickness.
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