CN109898064A - A kind of DLC/Me-C laminated film and preparation method thereof - Google Patents
A kind of DLC/Me-C laminated film and preparation method thereof Download PDFInfo
- Publication number
- CN109898064A CN109898064A CN201910249651.7A CN201910249651A CN109898064A CN 109898064 A CN109898064 A CN 109898064A CN 201910249651 A CN201910249651 A CN 201910249651A CN 109898064 A CN109898064 A CN 109898064A
- Authority
- CN
- China
- Prior art keywords
- film
- dlc
- metal
- preparation
- magnetron sputtering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A kind of DLC/Me-C laminated film and preparation method thereof, the laminated film are to be sequentially prepared Me-C film, DLC film using magnetron sputtering technique in metal or alloy matrix surface.Preparation method is that metal or alloy matrix is placed in magnetron sputtering apparatus, and Me-C film and DLC film is prepared in situ in metal or alloy matrix surface.The present invention deposits DLC using rf bias aid magnetron sputtering, expeditiously prepares film substrate bond strength height, the excellent DLC film of mechanical property, crocking resistance and corrosion resistance.The present invention selects Me-C transition zone as buffer layer, solves the problems, such as that DLC film internal stress is excessively high；Simultaneously before preparing Me-C buffer layer, using plasma bombardment substrate, amorphous modified layer is prepared, improves substrate surface state, reduce corrosion potential between matrix and the second phase, as a result confirms that amorphous layer/Me-C/DLC film has excellent mechanical property and corrosion resistance.
Description
Technical field
The invention discloses a kind of DLC/Me-C laminated films and preparation method thereof, belong to the preparation of DLC film material
Technical field.
Background technique
DLC film has excellent mechanics, crocking resistance, corrosion resistance, and can deposit at low temperature,
There is very big application potential in fields such as tribology, bio-medicals.But there are a characteristics for DLC film --- inside answer
Power is high, this makes, and film-substrate cohesion is very weak and thickness is extremely limited.DLC film must add transition zone thus
Or doping.And the performance of DLC film in a certain respect may then be weakened by adulterating.So finding a kind of suitable transition zone
It is the key that promote DLC film application.Transition zone not only influences the binding force of DLC film, to corrosion resistance
Can also influence it is very big, so in addition to matrix and DLC film all bond strengths it is high other than, must self-corrosion resistance it is big, no
Accelerate the corrosion of film or substrate.
Currently, DLC film mainly has cathodic arc deposition, plasma enhanced CVD (PECVD) and three kinds of magnetron sputtering
Preparation method.
Cathode arc is a kind of method for being used to depositing diamond-like film earliest, is under the action of strong electrical field, by carbon original
Son deposits in substrate, and existing major defect is: 1, there is the DLC film of preparation high internal stress to limit to
The thickness of DLC film is in nanoscale, it is difficult to add transition zone or doping；2, strong electrical field causes to have a large amount of graphite
Grain, which is shelled out, to be finally deposited in substrate, and the DLC film of high quality can not be obtained, and passes through addition Magnetic filter dress
Set to reduce graphite particle and can but filter a big chunk carbon ion or atom simultaneously and reduce deposition efficiency, and filter device complexity at
This height.Although magnetic filtering cathode arc can prepare the DLC film of high sp3C content, can not industrial applications, not by
To the favor of enterprise.
It is high that PECVD prepares DLC film deposition efficiency, and internal stress while DLC film sp3C content is high
It is relatively low, excellent combination property, however its doped chemical must be inputted in the form of atmosphere, this greatly hinders and prepares metal
Doped diamond film.
Magnetron sputtering mainly includes ion source aid magnetron sputtering and Dc bias magnetron sputtering；Ion source auxiliary magnetic control splashes
The DLC film bond strength height that can be prepared is penetrated, type is more, but slightly worse in comprehensive performance, ion source and its maintenance cost
It is high.And Dc bias magnetron sputtering is when preparing DLC film, target surface can generate and accumulate covering carbonization when due to sputtering
Object etc. and cause metallic target to insulate, the cation for bombarding target surface can be accumulated on target surface, cause target current potential rise so that between electrode
Electric field gradually become smaller, until glow discharge extinguish and sputter stop, simultaneously as DLC film electric conductivity itself is very poor, direct current is inclined
Pressure effect can then weaken or even no longer work, and cause film deposition thickness limited.In three kinds of different preparation methods, substrate is inclined
Pressure is all essential, but since the conductivity of DLC film is extremely low, and the prior art generallys use Dc bias, because
This, the influence with the increase substrate bias of deposition thickness to DLC film structure weakens, complete when thickness reaches 4 μm
Failure.
In addition, electrolyte is diffused into substrate along defect due to the defect of DLC film, micro-cell corrosion, corrosion speed are formed
Rate is even more than the substrate of no film protection fastly very much, and the long-term corrosion resistance of matrix for causing DLC film to be protected is bad.It is existing
There is technology although and have the structure using transition zone, but itself and unresolved potential problem between film layer, transition zone and matrix, it is resistance to
Corrosive nature is simultaneously not so good as people's will.
To sum up, that there are film-substrate cohesions is undesirable, film layer internal stress is big, corrosion resistance is undesirable, preparation for the prior art
The defects of at high cost, therefore, urgent need, provide a kind of effective solution.
Summary of the invention
The purpose of the present invention is to provide a kind of low-cost high-efficiencies to prepare the DLC film of excellent combination property
Method.
A kind of DLC/Me-C laminated film of the present invention is to use magnetron sputtering technique successively in metal or alloy matrix surface
Prepare Me-C film, DLC film.
A kind of DLC/Me-C laminated film of the present invention, prepares amorphous metal in metal or alloy matrix surface or alloy changes
After property layer, adopts magnetron sputtering technique and be sequentially prepared Me-C film, DLC film；Amorphous metal or alloy modification layer with a thickness of 5
~100nm.
A kind of DLC/Me-C laminated film of the present invention, metal or alloy matrix are selected from magnesium metal, aluminium, titanium, copper, iron and its conjunction
Gold.
A kind of DLC/Me-C laminated film of the present invention, the Me-C film are gradient-structure, in the Me-C film
Me content is successively successively decreased, and C content successively increases, and the Me in Me-C film, which is selected from, can form strong carbide element；It is chosen in particular from
One of Cr, Ti, Si, W, Mo.
A kind of preparation method of DLC/Me-C laminated film of the present invention, is that metal or alloy matrix is placed in magnetron sputtering to set
In standby, Me-C film and DLC film is prepared in situ in metal or alloy matrix surface.
A kind of preparation method of DLC/Me-C laminated film of the present invention, Me-C film are prepared using reaction magnetocontrol sputtering, with
For Me as sputtering target material, sputtering atmosphere is Ar and C2H2、CH4At least one of mixed atmosphere, sputtering source selected from radio frequency, in
One of frequency or DC power supply, in preparation process, control the content linear reduction of Me, and the flow of carbon-containing atmosphere is linearly increasing,
Prepare gradient Me-C film；Linearly increased rate is identical with the flow of carbon-containing atmosphere for the rate of the content linear reduction of Me；
Magnetron sputtering technique parameter are as follows:
Ar and C in mixed atmosphere2H2Or Ar and CH4Flow-rate ratio be 1-8, target power density 3.5-18.5Wcm-2,
Operating air pressure is 0.5-10Pa, sedimentation time 5-60min.
In preparation process, the content of Me gradually decreases to 0, and the content of carbon-containing atmosphere progressively increases to 100% from 0；
When prepared by DLC film, using graphite target or metal as sputtering target material, gas is sputtered when using graphite as target
Atmosphere is argon gas, and sputtering source is radio frequency, intermediate frequency or DC power supply；Magnetron sputtering technique parameter are as follows:
Target power density is 3.5-18.5Wcm-2, operating air pressure 0.25-5Pa, sedimentation time 5-60min apply inclined
Press 20V-300V.
When being sputtered using metallic target, sputtering atmosphere is Ar and C2H2Or Ar and CH4Mixed atmosphere, sputtering source is radio frequency
Or intermediate frequency power supply；Metal targets are selected from one of W, Mo, Ti, Cr, Si, Al or its alloy；Magnetron sputtering technique parameter are as follows:
Ar and C in mixed atmosphere2H2Or Ar and CH4Flow-rate ratio be 0.5-6, target power density 3.5-18.5W
cm-2, operating air pressure 0.5-10Pa, sedimentation time 5-60min are biased 20V-300V.
A kind of preparation method of DLC/Me-C laminated film of the present invention, when preparing DLC film, initial bias voltage 20-25V,
In magnetron sputtering process, primary bias was adjusted every 5-10 minutes, it is 5-30V that bias, which adjusts amplitude, when bias reaches 300V,
Stop bias adjusting, so that film has the gradient hardness constantly enhanced from inside to outside, reduces the residual stress in film, improve
Film wear resistance.
A kind of preparation method of DLC/Me-C laminated film of the present invention, is placed in magnetron sputtering apparatus for metal or alloy matrix
Sample base station on, the vacuum chamber of sample base station and ground connection, which insulate and connects, penetrates inclined power supply, applies to pure metal or alloy substrate
While bias, using plasma bombardment metal or alloy matrix surface, ion etching is carried out in metal or alloy matrix surface
With ion implanting, after obtaining surface reforming layer, Me-C is prepared in metal or alloy matrix surface modified layer using magnetron sputtering
Film and DLC film.
A kind of preparation method of DLC/Me-C laminated film of the present invention, plasma bombardment treatment process parameter are as follows:
It is biased 500-1000V, Ar plasma or Ar and N plasma, duration 10-60min；Surface is modified
Thickness 5~100nm of degree, surface reforming layer are amorphous layer.
The present invention proposes rf bias aid magnetron sputtering deposition DLC according to prior art many disadvantages, can to substrate
To apply different size of rf bias, film substrate bond strength height, mechanical property, crocking resistance can be expeditiously prepared
The excellent DLC film with corrosion resistance.Pass through change rf bias, thus it is possible to vary in DLC film sp2 with
Ratio between sp3 can carry out large-scale Effective Regulation to the structure of DLC film.Since the present invention can both lead to
It crosses and is passed through gas doping source, metallic target also can be used, transition zone is doped or prepared to DLC.The present invention has selected Me-C mistake
Layer is crossed as the buffer layer between DLC film and matrix, solves the problems, such as that DLC film internal stress is excessively high, further improves DLC
Performance, while before preparing Me-C transition zone, we use Ar, N plasma bombardment base using under firing frequency bias condition
Bottom is prepared for amorphous modified layer in substrate, and the amorphous modified layer of preparation has and improves substrate surface state and make that surface is more closely knit, mentions
Binding performance between high matrix and transition zone reduces the advantages such as corrosion potential between matrix and the second phase, as a result confirm amorphous layer/
Me-C/DLC film has excellent mechanical property and corrosion resistance.
The present invention has the advantage that due to using above-mentioned process and film layer structure
1, using rf bias aid magnetron sputtering technology of preparing, there is low-cost high-efficiency to prepare excellent combination property
The advantage of DLC film.This technology can use rf bias to substrate progress Ion Cleaning to promote binding force,
Also it can apply simultaneously substrate bias in the ionization level for promoting carbon-containing atmosphere with rf bias and promote mechanical property, and magnetic control target can
Deposition transition zone can also provide doped chemical, or prepare intrinsic DLC film using graphite target.
Radio frequency substrate bias it is a further advantage that will not make with the increase of film thickness biasing effect significantly under
Drop.Because radio-frequency power supply is alternating current, period alternating action is on target, and when sputtering target is in positive half cycle, electronics flows to target
Face, neutralizes the positive charge of its surface accumulation, and accumulates electronics, makes its surface that back bias voltage be presented, in the negative half period of radio-frequency voltage
Attract positive ion bombardment target when the phase, to enable sputtering process to continue progress, mitigate or prevent target poison ing phenomenon from occurring；Separately
Outside, radio-frequency voltage can pass through any kind of impedance, so when DLC film deposition is thicker, since DLC film itself is to radio frequency
The shield effectiveness of power supply is weaker so bias can be continued to without being influenced by thickness.
2, amorphous transition layer is prepared, film-substrate cohesion is effectively improved
1) amorphous modified layer, which improves substrate surface state, keeps surface more closely knit；
Due to the homogeneous single phase of amorphous layer, more uniformly, undulating composition is less for ingredient and tissue, without obvious crystal boundary, without the
The features such as two-phase particle or dislocation, can substantially improve parent metal or conjunction so preparing amorphous modified layer in matrix surface
The out-of-flatness state of gold surface eliminates matrix surface existing hole or the defects of hole, crackle, pin hole already, thus, substantially
Degree reduces the quantity of matrix surface corrosion nucleus defect, improves the corrosion resistance of composite film structure.
2) amorphous modified layer reduces the corrosion potential between matrix and the second phase；
Ion bombardment or etching in amorphous layer preparation process can make matrix or in which impurity element with similarly from
The cenotype for being chemically combined and generating similar structure occurs for son, increases the chemical uniformity of matrix surface, reduces script matrix
And the second corrosion potential between phase.In addition, amorphous layer can inhibit diffusion of the impurity element in matrix to matrix surface, keep away
Exempt from the case where becoming spot corrosion core due to impurity diffusion is to matrix surface.
3) matrix has corrosion-resistant cenotype to generate in amorphous modified layer preparation process:
During ion bombardment or ion implanting cenotype will be formed in conjunction with matrix atom.Such as N plasma bangs
It hits or the Mg3N2 cenotype for generating corrosion-resistant phase is corrosion-resistant phase by N ion implanting magnesium alloy matrix surface, to promote matrix
The corrosion resistance on surface.
4) due to the randomness of amorphous layer Elemental composition itself, so that amorphous layer inherently has preferable corrosion resistance
Can, meanwhile, the movement in amorphous layer of foreign ion or electrolyte intermediate ion also becomes extremely difficult, to hinder matrix corrosion
Generation.
The present invention uses plasma bombardment metal or alloy surface, due to using the bias of the even upper kilovolt of several hectovolts,
It is the plasma bombardment completed under larger bias condition, this will rise rapidly matrix surface temperature, matrix surface ingredient
Certain metallurgical bonding or matrix skin can occur at relatively high temperatures with plasma composition to be dissolved again at branch, etc.
Start bias anticlimax to very low value or directly closing to deposit transition zone after gas ions end of bombardment, due to plasma bombardment base
Body surface face whole process only about needs to continue 10-20 minutes or so, so matrix is quickly ramped up to its ambient enviroment while high temperature
Temperature will not be significantly raised, after end of bombardment, the matrix that surface is in high temperature is directly exposed to the lower surrounding ring of temperature
Cooling rapidly in border, so plasma bombardment is approximately the process that a rapid melting quickly solidifies, satisfaction forms amorphous layer institute
The fast cool condition needed.In addition, carrying out plasma bombardment matrix surface, energetic particle hits matrix under very high bias effect
Surface makes it generate a large amount of vacancy or interstitial atom, these point defects can under heat activation continuous travel motion simultaneously shape
At dislocation.Under the long period bombardment of high-energy, higher dislocation density will cause, due to every kind of metal or alloy surface
For the dislocation density that can be maintained there is the intrinsic limit, the dislocation density caused by plasma bombardment matrix surface is more than this
When the intrinsic limit, it will cause the collapse of matrix surface internal crystal framework and cause disordered state and matrix surface is finally made to form amorphous layer.
3, by amorphous transition layer, it is effectively improved film base current potential
The present invention is using plasma immersion ion injection technique as the pretreatment mode of deposition film, the energy needed by it
Measure it is low, it is high-efficient, it is easy to accomplish compound with other vacuum technologies of preparing, be very suitable for injection N ion.In addition to being changed to exceptionally,
Corrosion resistance can also be promoted by changing the structure of metal or alloy；So that metal or alloy has steadily in the long term resistance to
Corrosive nature.
4, the present invention is using continuous preparation Me-C/DLC film in situ, without obvious boundary, film layer between Me-C film layer and DLC
Between combine closely, basic zero defect or hole effectively block penetrating for electrolyte, greatly improve corrosion resistant
Corrosion energy；In addition, Me and C changes in gradient in Me-C/DLC film, i.e., from Me-C layers, into DLC film, C element content is gradually risen
Height, and metallic element Me content is gradually reduced to 0；Especially DLC film is prepared under the bias of variation, DLC film knot
Structure consecutive variations, the sp3 ratio being in particular in DLC film gradually rise, effectively reduce the residual stress of film, mention
High film quality and performance.
In summary, rf bias aid magnetron sputtering technology of the invention solves of the existing technology a variety of scarce
It falls into, there is apparent advantage.
Detailed description of the invention
Attached drawing 1 is the cross-sectional view of film prepared by the embodiment of the present invention 3；
Attached drawing 2 is the corresponding element line spectral distribution figure in white line position horizontal in attached drawing 1.
From attached drawing 1 as can be seen that gradient components DLC:H prepared by the present invention, thickness are about 4 μm, the film of preparation
Without new interface between layer.
It can be seen that film prepared by the present invention, C content are progressively increased to from 0 from the distribution diagram of element of attached drawing 2
100%, and Cr content is gradually lowered to 0, and is almost C entirely in 1 μ m of outermost layer.
Specific embodiment
Further detailed description is made to the present invention below with reference to embodiment and comparative example.
Embodiment 1: the compound film preparation of DLC/Me-C (ex situ deposition) containing amorphous layer
(1) preparation of Ar, N plasma modified layer
Using stainless steel as matrix, cleaned stainless steel base is put into sputtering chamber, substrate face graphite target, substrate connects
Radio-frequency power supply is connect, argon gas and nitrogen, flow-rate ratio 4:1 are passed through, shielding power supply is DC power supply, power 37W, work gas
1.1pa is pressed, applies substrate bias 700V, bombardment time 15min, obtains amorphous modified layer in matrix surface.
(2) preparation of the CrC transition zone of gradient Cr doping
Make stainless steel base face crome metal target, substrate connects radio-frequency power supply, while being passed through argon gas and acetylene, deposition process
In, argon flow is fixed as 16sccm, and acetylene flow-rate ratio is slowly increased 6 (sccm) from 0 (sccm), and bias is stepped up from 40V
To 110V.Shielding power supply is DC power supply, power 200W, operating air pressure 0.8pa, sedimentation time 15min；Due to using straight
Sputtering source is flowed, target surface will lead to metallic target insulation because generating and accumulating the carbide of covering when sputtering, with sputtering time
Extend, the chromium ion quantity in crome metal target will be gradually reduced up to being zero, realize the gradient distribution of Cr and C in film layer.
(3) prepared by DLC film
Substrate face graphite target, substrate connect radio-frequency power supply, are biased 130V, while being passed through argon gas and acetylene, flow
Than for 8:3, shielding power supply is radio-frequency power supply, power 200W, operating air pressure 7.0pa, sedimentation time 15min.
Embodiment 2: in-situ deposition (no amorphous layer) prepares DLC/Me-C composite membrane
(1) DLC film comprising transition zone of in-situ deposition gradient bias and ingredient makes stainless steel base face crome metal target,
Substrate connects radio-frequency power supply, while being passed through argon gas and acetylene, and in deposition process, argon flow is fixed as 16sccm, acetylene flow
From every 2 minutes increase 1sccm of 0 (sccm) up to increasing to 8 (sccm), while linearly increasing substrate bias, increase per minute from 25V
Add 5V until increasing to 140V.Shielding power supply is DC power supply, power 150W, operating air pressure 0.75Pa, sedimentation time
30min。
Embodiment 3: in-situ deposition containing amorphous layer prepares the compound film preparation of DLC/Me-C
(1) preparation of Ar, N plasma modified layer
Using stainless steel as matrix, cleaned stainless steel base is put into sputtering chamber, substrate face graphite target, substrate connects
Radio-frequency power supply is connect, argon gas and nitrogen, flow-rate ratio 4:1 are passed through, shielding power supply is DC power supply, power 37W, work gas
1.1pa is pressed, applies substrate bias 700V, bombardment time 15min, obtains amorphous modified layer in matrix surface.
(2) DLC film comprising transition zone of in-situ deposition gradient bias and ingredient
Make stainless steel base face crome metal target, substrate connects radio-frequency power supply, while being passed through argon gas and acetylene, deposition process
In, argon flow is fixed as 16sccm, acetylene flow from every 2 minutes increase 1sccm of 0 (sccm) up to increasing to 8 (sccm), together
When linearly increasing substrate bias, increase 5V per minute from 25V up to increasing to 140V.Shielding power supply is DC power supply, power supply function
Rate 150W, operating air pressure 0.75Pa, sedimentation time 30min；Due to using d.c. sputtering source, target surface is because generating and tiring out when sputtering
The carbide of product covering will lead to metallic target insulation, and with the extension of sputtering time, chromium ion quantity in crome metal target will be by
Step is reduced up to being zero, realizes the gradient distribution of Cr and C in film layer.
Embodiment 4:
Realize that Me-C gradient adjusts the DLC/Me-C composite membrane of preparation using radio-frequency sputtering source
(1) preparation of Ar, N plasma modified layer
Using stainless steel as matrix, cleaned stainless steel base is put into sputtering chamber, substrate face graphite target, substrate connects
Radio-frequency power supply is connect, argon gas and nitrogen, flow-rate ratio 4:1 are passed through, shielding power supply is DC power supply, power 37W, work gas
1.1pa is pressed, applies substrate bias 700V, bombardment time 15min, obtains amorphous modified layer in matrix surface.
(2) DLC film comprising transition zone of in-situ deposition gradient bias and ingredient
Make stainless steel base face crome metal target, substrate connects radio-frequency power supply, while being passed through argon gas and acetylene, deposition process
In, argon flow is fixed as 16sccm, acetylene flow from every 2 minutes increase 1sccm of 0 (sccm) up to increasing to 8 (sccm), together
When linearly increasing substrate bias, increase 5V per minute from 25V up to increasing to 140V.Shielding power supply is radio frequency source, power
150W adjusts and reduce radio-frequency power 20W in every 2 minutes, until radio-frequency power is zero, realizes the gradient distribution of Cr and C in film layer, work gas
Press 0.75Pa, sedimentation time 30min；
Comparative example 1: the DLC/Me-C composite membrane of no amorphous layer, ex situ deposition
(1) preparation of the CrC transition zone of gradient Cr doping
Make stainless steel base face crome metal target, substrate connects radio-frequency power supply, while being passed through argon gas and acetylene, deposition process
In, argon flow is fixed as 16sccm, and acetylene flow-rate ratio is slowly increased 6 (sccm) from 0 (sccm), and bias is stepped up from 40V
To 110V.Shielding power supply is DC power supply, power 200W, operating air pressure 0.8pa, sedimentation time 15min.
(2) prepared by DLC film
Substrate face graphite target, substrate connect radio-frequency power supply, are biased 130V, while being passed through argon gas and acetylene, flow
Than for 8:3, shielding power supply is radio-frequency power supply, power 200W, operating air pressure 7.0pa, sedimentation time 15min.
Comparative example 2: the DLC/Me-C film of no gradient components variation
(1) preparation of CrC transition zone
Substrate face chromium target, substrate connect radio-frequency power supply, are biased 50V, while being passed through argon gas and acetylene, flow-rate ratio is
16:3, shielding power supply are DC power supply, power 200W, operating air pressure 0.8pa, sedimentation time 15min.
(2) prepared by DLC film
Substrate face graphite target, substrate connect radio-frequency power supply, are biased 130V, while being passed through argon gas and acetylene, flow
Than for 8:3, shielding power supply is radio-frequency power supply, power 200W, operating air pressure 7.0pa, sedimentation time 15min.
Performance test results:
The properties of gained diamond-like carbon composite film are detected, the results are shown in Table 1.It is surveyed using Nanoindentation
The nano hardness of film is measured, uses constant load mode that compression distance is made to be no more than film integral thickness when testing nano hardness
1/10th.Wearability is characterized using friction and wear test, the use of mating plate is silicon nitride ball (diameter 4.2mm), is slided
Distance 8mm, load 8N, frequency 8Hz.By electro-chemical test, (test condition: three-electrode system, reference electrode are saturation Ag/
AgCl electrode, is Pt piece (15mm × 15mm × 0.1mm) to electrode, and sample is working electrode (exposed area 0.25cm2), electrolysis
Matter 3.5wt.%NaCl solution) understand its corrosion resistance, its corrosion current is obtained by Tafel polarization curve.
Table 1
Comprehensive comparison:
Nano hardness:
1 > comparative example of embodiment 3 > embodiment, 4 > embodiment, 2 > embodiment, 2 > comparative example 1
Coefficient of friction:
1 < comparative example of embodiment 4=embodiment 3 < embodiment, 2 < embodiment, 1 < comparative example 2；
Corrosion electric current density:
1 < comparative example of embodiment 3 < embodiment, 4 < embodiment, 2 < embodiment, 1 < comparative example 2.
Claims (9)
1. a kind of DLC/Me-C laminated film, which is characterized in that metal or alloy matrix surface using magnetron sputtering technique according to
Secondary preparation Me-C film, DLC film.
2. DLC/Me-C laminated film according to claim 1, which is characterized in that prepared in metal or alloy matrix surface
After amorphous metal or alloy modification layer, adopts magnetron sputtering technique and be sequentially prepared Me-C film, DLC film；Amorphous metal or
Alloy modification layer with a thickness of 5~100nm.
3. DLC/Me-C laminated film according to claim 1 or 2, which is characterized in that metal or alloy matrix is selected from gold
Belong to magnesium, aluminium, titanium, copper, iron and its alloy.
4. a kind of DLC/Me-C laminated film according to claim 3, which is characterized in that the Me-C film is gradient
Structure, Me content is successively successively decreased in the Me-C film, and C content successively increases, and the Me in Me-C film is selected from and can be formed
Strong carbide element；It is chosen in particular from one of Cr, Ti, Si, W, Mo.
5. a kind of preparation method of DLC/Me-C laminated film, is that metal or alloy matrix is placed in magnetron sputtering apparatus,
Me-C film and DLC film is prepared in situ in metal or alloy matrix surface.
6. a kind of preparation method of DLC/Me-C laminated film according to claim 5, it is characterised in that:
Me-C film is prepared using reaction magnetocontrol sputtering, and using Me as sputtering target material, sputtering atmosphere is Ar and C2H2, Ar and CH4In
At least one mixed atmosphere, sputtering source is selected from one of radio frequency, intermediate frequency or DC power supply, in preparation process, controls Me
Content linear reduction, the flow of carbon-containing atmosphere is linearly increasing, prepare gradient Me-C film；Magnetron sputtering technique parameter are as follows:
Ar and C in mixed atmosphere2H2Or Ar and CH4Flow-rate ratio be 1-8, target power density 3.5-18.5Wcm-2, work
Air pressure is 0.5-10Pa, sedimentation time 5-60min.
In preparation process, the content of Me gradually decreases to 0, and the content of carbon-containing atmosphere progressively increases to 100% from 0；
When prepared by DLC film, using graphite target or metal as sputtering target material, when using graphite as target sputtering atmosphere for
Argon gas, sputtering source are radio frequency, intermediate frequency or DC power supply；Magnetron sputtering technique parameter are as follows:
Target power density is 3.5-18.5Wcm-2, operating air pressure 0.25-5Pa, sedimentation time 5-60min are biased
20V-300V。
When being sputtered using metallic target, sputtering atmosphere is Ar and C2H2Or Ar and CH4Mixed atmosphere, sputtering source be radio frequency or in
Frequency power；Metal targets are selected from one of W, Mo, Ti, Cr, Si, Al or its alloy；Magnetron sputtering technique parameter are as follows:
Ar and C in mixed atmosphere2H2Or Ar and CH4Flow-rate ratio be 0.5-6, target power density 3.5-18.5Wcm-2, work
Making air pressure is 0.5-10Pa, and sedimentation time 5-60min is biased 20V-300V.
7. a kind of preparation method of DLC/Me-C laminated film according to claim 6, it is characterised in that: preparation DLC is thin
When film, initial bias voltage 20-25V in magnetron sputtering process, primary bias was adjusted every 5-10 minutes, bias adjusts amplitude and is
5-30V stops bias and adjusts when bias reaches 300V.
8. a kind of preparation method of DLC/Me-C laminated film, feature described according to claim 6 or 7 any one exist
In: on the sample base station that metal or alloy matrix is placed in magnetron sputtering apparatus, the vacuum chamber insulation of sample base station and ground connection is simultaneously
Inclined power supply is penetrated in connection, while being biased to pure metal or alloy substrate, using plasma bombardment metal or alloy matrix table
Face is carried out ion etching and ion implanting in metal or alloy matrix surface, after obtaining surface reforming layer, is existed using magnetron sputtering
Me-C film and DLC film are prepared in metal or alloy matrix surface modified layer.
9. a kind of preparation method of DLC/Me-C laminated film according to claim 8, it is characterised in that: plasma bombardment
Treatment process parameter are as follows:
It is biased 500-1000V, Ar plasma or Ar and N plasma, duration 10-60min；Surface reforming layer is thick
5~100nm is spent, surface reforming layer is amorphous layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910249651.7A CN109898064B (en) | 2019-03-29 | 2019-03-29 | DLC/Me-C composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910249651.7A CN109898064B (en) | 2019-03-29 | 2019-03-29 | DLC/Me-C composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109898064A true CN109898064A (en) | 2019-06-18 |
| CN109898064B CN109898064B (en) | 2020-02-04 |
Family
ID=66954163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910249651.7A Active CN109898064B (en) | 2019-03-29 | 2019-03-29 | DLC/Me-C composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109898064B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139430A (en) * | 2020-01-17 | 2020-05-12 | 兰州理工大学 | Textured diamond-like carbon-based film and preparation method thereof |
| CN113061845A (en) * | 2021-03-19 | 2021-07-02 | 安徽纯源镀膜科技有限公司 | Preparation process of ultra-black high-performance Ti-DLC coating |
| CN113151826A (en) * | 2021-04-23 | 2021-07-23 | 艾瑞森表面技术（苏州）股份有限公司 | Corrosion-resistant coating process and corrosion-resistant coating prepared by same |
| CN113403577A (en) * | 2021-06-23 | 2021-09-17 | 太原理工大学 | Method for improving binding force of Cu matrix and carbon-based film |
| CN113862613A (en) * | 2021-09-18 | 2021-12-31 | 美戈利(浙江)轨道交通研究院有限公司 | Amorphous gradient structure superhard DLC (diamond-like carbon) cutter coating and preparation method thereof and cutter |
| CN114086116A (en) * | 2021-11-17 | 2022-02-25 | 安徽通灵仿生科技有限公司 | Corrosion-resistant coating on surface of motor rotor of catheter pump and preparation process thereof |
| CN115261854A (en) * | 2022-07-30 | 2022-11-01 | 兰州理工大学 | Chemical corrosion resistant film layer compound protective coating and preparation method thereof |
| CN115466924A (en) * | 2022-10-26 | 2022-12-13 | 西安交通大学 | Rolling contact fatigue resistant film on surface of gear bearing set and preparation method thereof |
| CN116936840A (en) * | 2023-09-14 | 2023-10-24 | 国家电投集团氢能科技发展有限公司 | Functionally graded carbon-based coating for fuel cell metal bipolar plate and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1760172A2 (en) * | 2005-09-05 | 2007-03-07 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Diamondlike carbon hard multilayer film formed body and method for producing the same |
| CN101444985A (en) * | 2007-12-19 | 2009-06-03 | 中国人民解放军装甲兵工程学院 | Amorphous carbon coating and preparation method and application thereof |
| CN102623389A (en) * | 2011-01-31 | 2012-08-01 | 北京泰龙电子技术有限公司 | Method for preparing metal nitride barrier layer |
| CN102994968A (en) * | 2012-09-29 | 2013-03-27 | 蔡丛荣 | Anti-corrosive treatment method for aluminum alloy |
| CN103129023A (en) * | 2013-02-27 | 2013-06-05 | 武汉大学 | Corrosion and wear resistant Si/Si-DLC/DLC self-lubricating coat on inner wall of pipeline, and its preparation method |
| US20130209767A1 (en) * | 2012-02-15 | 2013-08-15 | Hauzer Techno Coating Bv | Coated article of martensitic steel and a method of forming a coated article of steel |
| US20140257494A1 (en) * | 2013-03-11 | 2014-09-11 | Kerstin Thorwarth | Coating for a titanium alloy substrate |
| CN105986202A (en) * | 2015-02-13 | 2016-10-05 | 有研稀土新材料股份有限公司 | Iron base non-crystalline material and preparation method thereof |
| CN107022745A (en) * | 2017-04-28 | 2017-08-08 | 星弧涂层新材料科技（苏州）股份有限公司 | Incrassation type laminated film and its film plating process based on DLC film |
| CN107400873A (en) * | 2017-07-26 | 2017-11-28 | 森科五金(深圳)有限公司 | A kind of DLC film and preparation method thereof |
| CN108690983A (en) * | 2017-04-10 | 2018-10-23 | 中国科学院宁波材料技术与工程研究所 | Wear-and corrosion-resistant Cr/CrAlSiN composite coatings, preparation method and application |
-
2019
- 2019-03-29 CN CN201910249651.7A patent/CN109898064B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1760172A2 (en) * | 2005-09-05 | 2007-03-07 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Diamondlike carbon hard multilayer film formed body and method for producing the same |
| CN101444985A (en) * | 2007-12-19 | 2009-06-03 | 中国人民解放军装甲兵工程学院 | Amorphous carbon coating and preparation method and application thereof |
| CN102623389A (en) * | 2011-01-31 | 2012-08-01 | 北京泰龙电子技术有限公司 | Method for preparing metal nitride barrier layer |
| US20130209767A1 (en) * | 2012-02-15 | 2013-08-15 | Hauzer Techno Coating Bv | Coated article of martensitic steel and a method of forming a coated article of steel |
| CN102994968A (en) * | 2012-09-29 | 2013-03-27 | 蔡丛荣 | Anti-corrosive treatment method for aluminum alloy |
| CN103129023A (en) * | 2013-02-27 | 2013-06-05 | 武汉大学 | Corrosion and wear resistant Si/Si-DLC/DLC self-lubricating coat on inner wall of pipeline, and its preparation method |
| US20140257494A1 (en) * | 2013-03-11 | 2014-09-11 | Kerstin Thorwarth | Coating for a titanium alloy substrate |
| CN105986202A (en) * | 2015-02-13 | 2016-10-05 | 有研稀土新材料股份有限公司 | Iron base non-crystalline material and preparation method thereof |
| CN108690983A (en) * | 2017-04-10 | 2018-10-23 | 中国科学院宁波材料技术与工程研究所 | Wear-and corrosion-resistant Cr/CrAlSiN composite coatings, preparation method and application |
| CN107022745A (en) * | 2017-04-28 | 2017-08-08 | 星弧涂层新材料科技（苏州）股份有限公司 | Incrassation type laminated film and its film plating process based on DLC film |
| CN107400873A (en) * | 2017-07-26 | 2017-11-28 | 森科五金(深圳)有限公司 | A kind of DLC film and preparation method thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139430B (en) * | 2020-01-17 | 2020-12-11 | 兰州理工大学 | Textured diamond-like carbon-based film and preparation method thereof |
| CN111139430A (en) * | 2020-01-17 | 2020-05-12 | 兰州理工大学 | Textured diamond-like carbon-based film and preparation method thereof |
| CN113061845B (en) * | 2021-03-19 | 2023-04-07 | 安徽纯源镀膜科技有限公司 | Preparation process of ultra-black high-performance Ti-DLC coating |
| CN113061845A (en) * | 2021-03-19 | 2021-07-02 | 安徽纯源镀膜科技有限公司 | Preparation process of ultra-black high-performance Ti-DLC coating |
| CN113151826A (en) * | 2021-04-23 | 2021-07-23 | 艾瑞森表面技术（苏州）股份有限公司 | Corrosion-resistant coating process and corrosion-resistant coating prepared by same |
| CN113403577A (en) * | 2021-06-23 | 2021-09-17 | 太原理工大学 | Method for improving binding force of Cu matrix and carbon-based film |
| CN113862613A (en) * | 2021-09-18 | 2021-12-31 | 美戈利(浙江)轨道交通研究院有限公司 | Amorphous gradient structure superhard DLC (diamond-like carbon) cutter coating and preparation method thereof and cutter |
| CN114086116A (en) * | 2021-11-17 | 2022-02-25 | 安徽通灵仿生科技有限公司 | Corrosion-resistant coating on surface of motor rotor of catheter pump and preparation process thereof |
| CN115261854A (en) * | 2022-07-30 | 2022-11-01 | 兰州理工大学 | Chemical corrosion resistant film layer compound protective coating and preparation method thereof |
| CN115261854B (en) * | 2022-07-30 | 2023-09-29 | 兰州理工大学 | Chemical corrosion resistant film compound protective coating and preparation method thereof |
| CN115466924A (en) * | 2022-10-26 | 2022-12-13 | 西安交通大学 | Rolling contact fatigue resistant film on surface of gear bearing set and preparation method thereof |
| CN115466924B (en) * | 2022-10-26 | 2024-01-16 | 西安交通大学 | Rolling contact fatigue resistant film on surface of gear bearing group and preparation method thereof |
| CN116936840A (en) * | 2023-09-14 | 2023-10-24 | 国家电投集团氢能科技发展有限公司 | Functionally graded carbon-based coating for fuel cell metal bipolar plate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109898064B (en) | 2020-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109898064A (en) | A kind of DLC/Me-C laminated film and preparation method thereof | |
| CN106374116B (en) | High-entropy alloy composite coating and technique on a kind of fuel battery metal double polar plate | |
| Feng et al. | C/CrN multilayer coating for polymer electrolyte membrane fuel cell metallic bipolar plates | |
| Jin et al. | Effects of Mo content on the interfacial contact resistance and corrosion properties of CrN coatings on SS316L as bipolar plates in simulated PEMFCs environment | |
| Lee et al. | Corrosion and electrical properties of CrN-and TiN-coated 316L stainless steel used as bipolar plates for polymer electrolyte membrane fuel cells | |
| Bi et al. | Mechanisms of growth, properties and degradation of amorphous carbon films by closed field unbalanced magnetron sputtering on stainless steel bipolar plates for PEMFCs | |
| CN103199279B (en) | The doping type multi-gradient coating of fuel battery metal double polar plate | |
| Yi et al. | Cr–N–C multilayer film on 316L stainless steel as bipolar plates for proton exchange membrane fuel cells using closed field unbalanced magnetron sputter ion plating | |
| CN109755592A (en) | A kind of metal double polar plates and preparation method thereof and fuel cell | |
| CN109913771A (en) | A kind of VAlTiCrSi high-entropy alloy film and its application under briny environment | |
| CN112501569B (en) | Surface gradient high-entropy alloy layer and preparation method thereof | |
| Jin et al. | Effect of Ni content on the electrical and corrosion properties of CrNiN coating in simulated proton exchange membrane fuel cell | |
| CN110468381B (en) | High-frequency oscillation pulse magnetron sputtering method | |
| CN106282887B (en) | The in-situ preparation method of the dispersed particle-strengthened alloy coat of oxide crystallite | |
| CN108165944B (en) | A kind of super thick Ti2The preparation method of AlC coating | |
| CN108274009B (en) | Cr target material repairing method | |
| CN104087902B (en) | Insulating coating of metal material surface and preparation method thereof | |
| CN114231925A (en) | Fuel cell metal bipolar plate composite coating and preparation method thereof | |
| CN110923650B (en) | DLC coating and preparation method thereof | |
| CN109898051A (en) | A kind of wear-resistant corrosion resistant DLC/SiNxLaminated film and preparation method thereof | |
| CN110783594B (en) | Metal bipolar plate, preparation method thereof and fuel cell | |
| CN104109830B (en) | Surface hafnium-infiltrated austenitic stainless steel resistant to high temperature and preparation method thereof | |
| CN205035458U (en) | Stainless steel surface ion silicizing device | |
| CN104109842A (en) | Surface hafnium-permeated+carburized high-temperature-resistant stainless steel and preparation method thereof | |
| CN107130224B (en) | A kind of radiation resistance coating production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210331 Address after: 518000 5th floor, building 7, xinxintian Industrial Zone, Xinsha Road, Shayi community, Shajing street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Fuji Vacuum Technology Co.,Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210531 Address after: 1233, building 8, yinguyuan, 528 Jinxing Middle Road, Yuelu District, Changsha City, Hunan Province 410000 Patentee after: Hunan Xinfeng Technology Co.,Ltd. Address before: 518000 5th floor, building 7, xinxintian Industrial Zone, Xinsha Road, Shayi community, Shajing street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Fuji Vacuum Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |