CN110158035A - The metal-metal nitride laminated coating of high temperature resistant marine environment and preparation - Google Patents
The metal-metal nitride laminated coating of high temperature resistant marine environment and preparation Download PDFInfo
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- CN110158035A CN110158035A CN201910569350.2A CN201910569350A CN110158035A CN 110158035 A CN110158035 A CN 110158035A CN 201910569350 A CN201910569350 A CN 201910569350A CN 110158035 A CN110158035 A CN 110158035A
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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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- C23C14/0021—Reactive sputtering or evaporation
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- 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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- C23C14/0641—Nitrides
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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
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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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Abstract
The present invention relates to titanium alloy high-temperature protective coating field, the metal-metal nitride laminated coating and preparation method of specially a kind of high temperature resistant marine environment.Laminated coating is formed on matrix by Ti sublayer and TiN sublayer alternating deposit, is TiN layer close to matrix and top layer, and matrix is Ti6Al4V titanium alloy；In laminated coating, each TiN molecular layers thick is 1.7~2.0 μm, and each Ti molecular layers thick is that 0.1~1.0 μm of total number of plies is odd number in 13~21 layers.The preparation of the laminated coating includes: matrix cleaning and TiN sublayer and Ti sublayer alternating deposit.The present invention prepares the thick Ti/TiN laminated coating of different sublayer ratios on titanium alloy substrate, this type coating and substrate combinating strength are good, coating has higher thickness, by increasing the diffusion path of corrosive medium and reducing fault of construction, improves the resistance to high temperature corrosion performance of titanium alloy substrate.
Description
Technical field:
The present invention relates to titanium alloy high-temperature protective coating field, specially a kind of metal-of high temperature resistant marine environment
Metal nitride laminated coating and preparation method.
Background technique:
Titanium alloy density is low, intensity is high, is the critical material of aero-engine compressor.But as medium high-temperature service
Gas compressor blade sheet material, it has following shortcoming: first is that hardness is lower, anti-erosion property is poor, second is that elevated temperature corrosion resistant
It can be insufficient.Especially it is served in the aircraft engine of marine environment, the titanium alloy member of compressor is by or high temperature Cl-、O
Collaboration with vapor etc. is corroded, and corrosion rate is not only much higher than the oxidation rate of simple air, but also in lower temperature
Under, alloy sub-surface will generate thick brittleness dissolved oxygen layer, and the mechanical property of alloy is caused to be remarkably decreased.
Metal nitride coatings have excellent Anti-erosion and high-temperature corrosion resistance performance, show very in terms of titanium alloy protection
Good application prospect, is especially suitable for being served in the titanium alloy member of the aircraft compressor of marine environment.But it is long in higher temperature
Time is exposed in corrosive environment, and local accelerated corrosion occurs for coating, and leads to the heavy corrosion of its lower substrate, the needle in coating
The defects of hole, molten drop is often the source for inducing accelerated corrosion.
The thickness for increasing coating can improve the corrosion resistance of coating.But as a kind of ceramic coating, in nitride coatings
Higher internal stress and intrinsic brittleness reduce the binding performance of coating and matrix with the increase of thickness, and single layer nitride applies
The trend that layer is peeled off when thickness is more than 7 μm significantly increases；Moreover, coating and matrix mismatch when being on active service under high temperature environment
Thermal expansion coefficient will lead to and generate biggish tensile stress in coating, easily make coating cracking, deteriorate corrosion resistance, it is difficult to ensure apply
The extended protection performance of layer.
Opposite single layer nitride coatings, metal-nitride laminated coating have lower internal stress and good with matrix
Bond strength, combine high mechanical property and corrosion resistance.Research shows that (Surf.Coat.Technol.258 (2014)
102-107 and Surf.Coat.Technol.282 (2015) 78-85.), multilayered structure nitride coatings are in room temperature aqueous solution
Corrosion resistance be better than signal layer coating, reason essentially consists in: corrosive medium the molten drop pin hole the defects of in migration be suppressed, or
Person, which says, reduces penetrability defects count.
Ti/TiN laminated coating has the advantages that low internal stress, good coating/substrate combinating strength, strong mechanical performance,
And it is less about the corrosion report of thick Ti/TiN laminated coating high temperature resistant marine environment both at home and abroad.
Summary of the invention:
The purpose of the present invention is to provide a kind of metal-metal nitride laminated coating of high temperature resistant marine environment and
Preparation method can solve titanium alloy high-temperature etching problem, provide a kind of thinking for the high temperature protection of aerial motor spare part.
The technical scheme is that
A kind of metal-metal nitride laminated coating of high temperature resistant marine environment, laminated coating is by Ti sublayer and TiN
Sublayer alternating deposit is formed on matrix, is TiN layer close to matrix and top layer.
The metal-metal nitride laminated coating of the high temperature resistant marine environment, each TiN molecular layers thick are
1.7~2.0 μm, each Ti molecular layers thick is 0.1~1.0 μm, and total number of plies of metal/metal nitride laminated coating is 13~21
Odd number in layer.
The metal-metal nitride laminated coating of the high temperature resistant marine environment, matrix Ti6Al4V.
The preparation method of the metal-metal nitride laminated coating of the high temperature resistant marine environment, specifically includes
Steps are as follows:
(1) matrix cleans
After the grinding of Ti6Al4V titanium alloy substrate, polishing treatment, it is put into the mixing of 1:2~4 by volume of acetone and ethyl alcohol
In solution, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；The sample handled well is suspended on specimen holder
On, it is put into ion plating vacuum chamber, closes room door, carry out icon bombardment cleaning using ion plating equipment；
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, it is negative that Ti6Al4V titanium alloy substrate applies pulse
Bias opens cathode Ti target current, starts the deposition of TiN sublayer；Then depositing Ti sublayer keeps Ti target current constant, closes
N2, it is passed through Ar, adjusts Ti6Al4V titanium alloy substrate negative bias values, carries out Ti sublayer deposition；The TiN in later deposition process
Sublayer and Ti sublayer successively alternating deposit；After to the last layer Ti sublayer deposition, one layer of TiN is as outermost layer for redeposition.
The preparation method of the metal-metal nitride laminated coating of the high temperature resistant marine environment, step (1)
In, before icon bombardment cleaning, being evacuated to vacuum degree is 7 × 10-3~10 × 10-3Pa, be passed through Ar maintain vacuum degree 0.2~
It is 850~950V that 0.5Pa, Ti6Al4V titanium alloy substrate, which apply negative bias values, and duty ratio is 30~60%, icon bombardment cleaning
Time is 3~10min.
The preparation method of the metal-metal nitride laminated coating of the high temperature resistant marine environment, step (2)
In, Ti target purity is 99.99wt% or more, and it is highly 50~60mm, the volume of argon gas and nitrogen is pure that diameter, which is 80~120mm,
Degree is 99.99% or more.
The preparation method of the metal-metal nitride laminated coating of the high temperature resistant marine environment, step (2)
In, TiN sublayer deposition parameter are as follows: Ti target current 60~80A, N2Pressure is 1.4~2.0Pa, and negative bias values are 550~600V,
Sedimentation time is 18~21min, and duty ratio is that Ti and N atomic ratio is 1:1 in 20~30%, TiN sublayer.
The preparation method of the metal-metal nitride laminated coating of the high temperature resistant marine environment, step (2)
In, Ti sublayer deposition parameter are as follows: Ti target current 60~80A, Ar pressure is 0.2~0.5Pa, and negative bias values are 50~100V, is sunk
The product time is 2~21min, and duty ratio is 20~30%.
The preparation method of the metal-metal nitride laminated coating of the high temperature resistant marine environment, step (1) is extremely
(2) in deposition process, Ti target and Ti6Al4V titanium alloy substrate distance are 17~22cm, and specimen holder is with 3~6rpm speed rotation.
The preparation method of the metal-metal nitride laminated coating of the high temperature resistant marine environment, coating deposition
In the process, the titanium alloy-based temperature of Ti6Al4V is 300 DEG C ± 20 DEG C.
Design philosophy of the invention is:
The present invention prepares the thick Ti/TiN laminated coating of different sublayer ratios, this type coating and matrix on titanium alloy substrate
Bond strength is good, and coating has higher thickness, by increasing the diffusion path of corrosive medium and reducing fault of construction, improves
The resistance to high temperature corrosion performance of titanium alloy substrate.
Advantages of the present invention and beneficial effect are:
1. the present invention is by periodically introducing metal Ti layers, simultaneously laminated coating is effectively reduced in adsorbing nitride layer internal stress
The good thickness Ti/TiN laminated coating of film substrate bond strength can be obtained in stress.
2. thickness Ti/TiN laminated coating prepared by the present invention extends the time that corrosive medium reaches matrix by its high thickness,
Improve the resistance to high temperature corrosion performance of matrix.The Ti layer of introducing is isometric crystal structure, breaks the continuous columnar crystal structure of TiN layer, from
And inhibit the formation of penetrability defect such as crackle, micropore and crystal boundary, corrosive medium can be prevented to arrive at titanium alloy along penetrability defect
Matrix makes coating play long-life, high-temperature corrosion protection.
3. the present invention uses common ion plating vapor deposition means, preparation process is easy, is easy to implement industrialized production
Using.
4. metal/metal nitride laminated coating of the present invention has good marine environment resistant to high temperatures, as Ti
When layer is with a thickness of 0.1 μm, marine environment best performance resistant to high temperatures.
Detailed description of the invention:
Fig. 1 is the laminated coating surface Ti/TiN (a) prepared by embodiment 1 and section (b) scanning electron microscope pattern photo.
Fig. 2 is that the corrosion of Ti/TiN laminated coating prepared by embodiment 1 rear surface (a) and section (b) scanning electron microscope pattern shine
Piece.
Fig. 3 is the laminated coating surface Ti/TiN (a) prepared by embodiment 5 and section (b) scanning electron microscope pattern photo.
Fig. 4 is that the corrosion of Ti/TiN laminated coating prepared by embodiment 5 rear surface (a) and section (b) scanning electron microscope pattern shine
Piece.
Fig. 5 is the laminated coating surface Ti/TiN (a) prepared by embodiment 6 and section (b) scanning electron microscope pattern photo.
Fig. 6 is that the corrosion of Ti/TiN laminated coating prepared by embodiment 6 rear surface (a) and section (b) scanning electron microscope pattern shine
Piece.
Fig. 7 is the signal layer coating surface TiN (a) prepared by comparative example and section (b) scanning electron microscope pattern photo.
Fig. 8 is the corrosion of TiN signal layer coating prepared by comparative example rear surface (a) and section (b) scanning electron microscope pattern photo.
Fig. 9 is 1,5,10 gained Ti/TiN laminated coating of embodiment and comparative example surrosion curve.In figure, abscissa t
Oxidization time (h) is represented, ordinate Δ m/s represents oxidation weight gain (mg/cm2)。
Figure 10 is X-ray diffraction (XRD) result after 1,5,10 gained Ti/TiN laminated coating of embodiment and comparative example corrosion
Figure.
Specific embodiment:
In the specific implementation process, the metal/metal nitride laminated coating of high temperature resistant marine environment of the present invention and
Preparation preparation used, characterization and measuring instrument are as follows:
Ion plating equipment, DH-4 type, Shenyang northern new railway space vacuum technique Co., Ltd；
Scanning electron microscope, Philips FEI-Inspect F type, Philips Radio&Video Co., Spain；
X-ray diffractometer, D/MAX-RA type X-ray energy spectrometer (XRD), Rigaku motor；
High temperature corrosion thermogravimetric analyzer, VERSA THERMHM type, Metal Inst., Chinese Academy of Sciences.
Below by specific embodiment, the present invention is described in further detail, but is not intended to limit the present invention.
Embodiment 1
In the present embodiment, the metal/metal nitride laminated coating of high temperature resistant marine environment, by Ti sublayer and TiN
What sublayer alternating deposit was formed on Ti6Al4V matrix, be TiN layer close to matrix and top layer, each TiN molecular layers thick is
2.0 μm, each Ti molecular layers thick is 0.1 μm, and total number of plies is 17 layers.
The preparation method of the metal/metal nitride laminated coating of above-mentioned high temperature resistant marine environment, specifically include as
Lower step:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:2 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；So
Icon bombardment cleaning is carried out using ion plating equipment afterwards, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder, is put
Enter in ion plating vacuum chamber, close room door, being evacuated to vacuum degree is 7.0 × 10-3After Pa, it is passed through Ar, vacuum degree is maintained to exist
0.5Pa, it is 950V that matrix, which applies negative bias values, and duty ratio 30% carries out 3min icon bombardment cleaning to matrix.
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 1.4Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current in 600V, is set as 60A, starts the deposition of TiN sublayer, and the time is
18.5min, duty ratio are set as 20%, and specimen holder keeps rotation, and speed keeps 3rpm, Ti:N=1:1 (atom in gained sublayer
Than)；Then depositing Ti sublayer keeps Ti target current 70A constant, closes N2, it is passed through Ar, control pressure is in 0.2Pa or so, matrix
Negative bias values are changed to 100V, and sedimentation time is controlled in 2min, and duty ratio is set as 20%, specimen holder keep 5rpm from revolving speed
Degree.TiN sublayer and Ti sublayer successively alternating deposit in later deposition process；After to the last layer Ti sublayer deposition,
One layer of TiN is as outermost layer for redeposition.Matrix heating temperature is 300 DEG C ± 20 DEG C, cathode targets and Ti6Al4V titanium alloy substrate
Distance is 17cm, and Ti target purity is 99.99wt%, Ti target diameter 80mm, height 55mm.
As shown in Fig. 1 (a)-(b), to deposited laminated coating carry out morphology observation, coating surface there are a small amount of size compared with
Small molten drop, cross-section observation find brilliant white be Ti sublayer, dark gray be TiN sublayer, structure even compact, laminated coating with
Ti6Al4V matrix is well combined, and does not find cracking, lamination.Found after 450 DEG C of corrosion 100h, surrosion total amount compared with
It is small, gentle growth (Fig. 9) of increasing weight in corrosion process.As shown in Fig. 2 (a)-(b), corrosion rear surface is complete, and one layer of Surface Creation is
Even, continuous, stable r-TiO2(Figure 10), coat inside is complete, stablizes, and it is good anticorrosive to show that the embodiment coating has
Property.
Embodiment 2
In the present embodiment, the metal/metal nitride laminated coating of high temperature resistant marine environment, by Ti sublayer and TiN
What sublayer alternating deposit was formed on Ti6Al4V matrix, be TiN layer close to matrix and top layer, each TiN molecular layers thick is
2.0 μm, each Ti molecular layers thick is 0.2 μm, and total number of plies is 15 layers.
The preparation method of the metal/metal nitride laminated coating of above-mentioned high temperature resistant marine environment, specifically include as
Lower step:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:2.5 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；
Then icon bombardment cleaning is carried out using ion plating equipment, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder,
It is put into ion plating vacuum chamber, closes room door, being evacuated to vacuum degree is 8.5 × 10-3After Pa, it is passed through Ar, maintains vacuum degree
In 0.5Pa, it is 950V that matrix, which applies negative bias values, and duty ratio 40% carries out 5min icon bombardment cleaning to matrix.
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 1.5Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current in 580V, is set as 65A, starts the deposition of TiN sublayer, and 19min is accounted for
For sky than being set as 25%, specimen holder keeps rotation, and speed keeps 4rpm, element ratio Ti:N=1:1 (atomic ratio) in gained sublayer；
Then depositing Ti sublayer keeps Ti target current 65A constant, closes N2, it is passed through Ar, control pressure is in 0.3Pa or so, matrix negative bias
Pressure value is changed to 80V, and sedimentation time is controlled in 2.5min, and duty ratio is set as 25%, and specimen holder keeps the rotational velocity of 4rpm.?
TiN sublayer and Ti sublayer successively alternating deposit in later deposition process；It is redeposited after to the last layer Ti sublayer deposition
One layer of TiN is as outermost layer.Matrix heating temperature is 300 DEG C ± 20 DEG C, and cathode targets are with Ti6Al4V titanium alloy substrate distance
18cm, Ti target purity are 99.99wt%, Ti target diameter 90mm, height 55mm.
Morphology observation, the coating surface molten drop different there are certain amount, size, section are carried out to deposited laminated coating
Observation discovery brilliant white is Ti sublayer, and dark gray is TiN sublayer, and there are molten drop defect, laminated coating and Ti6Al4V matrixes for inside
It is well combined, does not find cracking, lamination.It is found after 450 DEG C of corrosion 100h, surrosion total amount is smaller, corrosion process
It is middle to increase weight slowly (Fig. 9).It is complete to corrode rear surface, one layer of uniform, continuous, stable r-TiO of Surface Creation2(Figure 10), coating
It is internal complete, stable, show that the embodiment coating has good corrosion resistance.
Embodiment 3
In the present embodiment, the metal/metal nitride laminated coating of high temperature resistant marine environment, by Ti sublayer and TiN
What sublayer alternating deposit was formed on Ti6Al4V matrix, be TiN layer close to matrix and top layer, each TiN molecular layers thick is
1.9 μm, each Ti molecular layers thick is 0.3 μm, and total number of plies is 15 layers.
The preparation method of the metal/metal nitride laminated coating of above-mentioned high temperature resistant marine environment, specifically include as
Lower step:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:3 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；So
Icon bombardment cleaning is carried out using ion plating equipment afterwards, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder, is put
Enter in ion plating vacuum chamber, close room door, being evacuated to vacuum degree is 9.0 × 10-3After Pa, it is passed through Ar, vacuum degree is maintained to exist
0.4Pa, it is 900V that matrix, which applies negative bias values, and duty ratio 50% carries out 7min icon bombardment cleaning to matrix.
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 1.6Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current in 560V, is set as 70A, starts the deposition of TiN sublayer, 19.5min,
Duty ratio is set as 25%, and specimen holder keeps rotation, and speed keeps 5rpm, Ti:N=1:1 (atomic ratio) in gained sublayer；Then
Depositing Ti sublayer keeps Ti target current 70A constant, closes N2, it is passed through Ar, control pressure is in 0.4Pa or so, substrate negative voltage value
It is changed to 70V, sedimentation time is controlled in 3.5min, and duty ratio is set as 25%, and specimen holder keeps the rotational velocity of 5rpm.Afterwards
Deposition process in TiN sublayer and Ti sublayer successively alternating deposit；It is one layer redeposited after to the last layer Ti sublayer deposition
TiN is as outermost layer.Matrix heating temperature is 300 DEG C ± 20 DEG C, and cathode targets are with Ti6Al4V titanium alloy substrate distance
19cm, Ti target purity are 99.99wt%, Ti target diameter 100mm, height 55mm.
Morphology observation is carried out to deposited laminated coating, there are certain amount, larger-size molten drop, sections for coating surface
Observation discovery brilliant white is Ti sublayer, and dark gray is TiN sublayer, and there are molten drop defect, laminated coating and Ti6Al4V matrixes for inside
It is well combined, does not find cracking, lamination.It is found after 450 DEG C of corrosion 100h, surrosion becomes larger, and increases in corrosion process
Accelerate again, molten drops on surface is corroded, one layer of uniform r-TiO of Surface Creation2, coat inside is complete, stablizes, and shows the embodiment
Coating has preferable corrosion resistance.
Embodiment 4
In the present embodiment, the metal/metal nitride laminated coating of high temperature resistant marine environment, by Ti sublayer and TiN
What sublayer alternating deposit was formed on Ti6Al4V matrix, be TiN layer close to matrix and top layer, each TiN molecular layers thick is
1.8 μm, each Ti molecular layers thick is 0.4 μm, and total number of plies is 13 layers.
The preparation method of the metal/metal nitride laminated coating of above-mentioned high temperature resistant marine environment, specifically include as
Lower step:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:3.5 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；
Then icon bombardment cleaning is carried out using ion plating equipment, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder,
It is put into ion plating vacuum chamber, closes room door, being evacuated to vacuum degree is 9.5 × 10-3After Pa, it is passed through Ar, maintains vacuum degree
In 0.3Pa, it is 850V that matrix, which applies negative bias values, and duty ratio 60% carries out 10min icon bombardment cleaning to matrix.
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 1.7Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current in 560V, is set as 75A, starts the deposition of TiN sublayer, 19.5min,
Duty ratio is set as 30%, and specimen holder keeps rotation, and speed keeps 6rpm, Ti:N=1:1 (atomic ratio) in gained sublayer；Then
Depositing Ti sublayer keeps Ti target current 75A constant, closes N2, it is passed through Ar, control pressure is in 0.35Pa or so, substrate negative voltage
Value is changed to 60V, and sedimentation time is controlled in 4min, and duty ratio is set as 30%, and specimen holder keeps the rotational velocity of 6rpm.Afterwards
Deposition process in TiN sublayer and Ti sublayer successively alternating deposit；It is one layer redeposited after to the last layer Ti sublayer deposition
TiN is as outermost layer.Matrix heating temperature is 300 DEG C ± 20 DEG C, and cathode targets are with Ti6Al4V titanium alloy substrate distance
20cm, Ti target purity are 99.99wt%, Ti target diameter 110mm, height 55mm.
Morphology observation, coating surface there are quantity more, larger-size molten drop, section are carried out to deposited laminated coating
Observation discovery brilliant white is Ti sublayer, and dark gray is TiN sublayer, and there are molten drop defect, laminated coating and Ti6Al4V matrixes for inside
It is well combined, does not find cracking, lamination.It is found after 450 DEG C of corrosion 100h, surrosion becomes larger, and increases in corrosion process
Accelerate again, molten drops on surface is corroded, Surface Creation r-TiO2Corrosion layer, coat inside locally corrode, the embodiment coating
Corrosion resistance decline.
Embodiment 5
In the present embodiment, the metal/metal nitride laminated coating of high temperature resistant marine environment, by Ti sublayer and TiN
What sublayer alternating deposit was formed on Ti6Al4V matrix, be TiN layer close to matrix and top layer, each TiN molecular layers thick is
1.8 μm, each Ti molecular layers thick is 0.5 μm, and total number of plies is 17 layers.
The preparation method of the metal/metal nitride laminated coating of above-mentioned high temperature resistant marine environment, specifically include as
Lower step:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:4 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；So
Icon bombardment cleaning is carried out using ion plating equipment afterwards, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder, is put
Enter in ion plating vacuum chamber, close room door, being evacuated to vacuum degree is 1 × 10-2After Pa, it is passed through Ar, vacuum degree is maintained to exist
0.3Pa, it is 900V that matrix, which applies negative bias values, and duty ratio 60% carries out 3min icon bombardment cleaning to matrix.
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 1.8Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current in 550V, is set as 80A, starts the deposition of TiN sublayer, 20.5min,
Duty ratio is set as 20%, and specimen holder keeps rotation, and speed keeps 5rpm, Ti:N=1:1 (atomic ratio) in gained sublayer；Then
Depositing Ti sublayer keeps Ti target current 80A constant, closes N2, it is passed through Ar, control pressure is in 0.4Pa or so, substrate negative voltage value
It is changed to 50V, sedimentation time is controlled in 5min, and duty ratio is set as 20%, and specimen holder keeps the rotational velocity of 5rpm.Afterwards
TiN sublayer and Ti sublayer successively alternating deposit in deposition process；It is one layer redeposited after to the last layer Ti sublayer deposition
TiN is as outermost layer.Matrix heating temperature is 300 DEG C, and cathode targets and Ti6Al4V titanium alloy substrate distance are 21cm, Ti target
Purity is 99.99wt%, Ti target diameter 120mm, height 50mm.
As shown in Fig. 3 (a)-(b), morphology observation, coating surface there are quantity more, ruler are carried out to deposited laminated coating
Very little biggish molten drop, cross-section observation find that brilliant white is Ti sublayer, and dark gray is TiN sublayer, and there are larger-size molten for inside
Defect is dripped, laminated coating is well combined with Ti6Al4V matrix, does not find cracking, lamination.As shown in Fig. 4 (a)-(b), warp
It being found after 450 DEG C of corrosion 100h, surrosion becomes larger, and increases weight and accelerates in corrosion process, and it cracks and peels off after the big molten drop corrosion in surface,
Form etch pit, Surface Creation r-TiO2Serious internal corrosion locally occurs for corrosion layer (Figure 10), coat inside, the coating corrosion resistance
It is poor.
Embodiment 6
In the present embodiment, the metal/metal nitride laminated coating of high temperature resistant marine environment, by Ti sublayer and TiN
What sublayer alternating deposit was formed on Ti6Al4V matrix, be TiN layer close to matrix and top layer, each TiN molecular layers thick is
1.7 μm, each Ti molecular layers thick is 1.0 μm, and total number of plies is 15 layers.
The preparation method of the metal/metal nitride laminated coating of above-mentioned high temperature resistant marine environment, specifically include as
Lower step:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:2 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；So
Icon bombardment cleaning is carried out using ion plating equipment afterwards, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder, is put
Enter in ion plating vacuum chamber, close room door, being evacuated to vacuum degree is 1 × 10-2After Pa, it is passed through Ar, vacuum degree is maintained to exist
0.2Pa, it is 950V that matrix, which applies negative bias values, and duty ratio 50% carries out 5min icon bombardment cleaning to matrix.
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 2.0Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current in 600V, is set as 70A, starts the deposition of TiN sublayer, and 21min is accounted for
For sky than being set as 30%, specimen holder keeps rotation, and speed keeps 5rpm, Ti:N=1:1 (atomic ratio) in gained sublayer；Then it sinks
Product Ti sublayer, keeps Ti target current 70A constant, closes N2, it is passed through Ar, control pressure changes in 0.5Pa or so, substrate negative voltage value
For 50V, sedimentation time is controlled in 11min, and duty ratio is set as 30%, and specimen holder keeps the rotational velocity of 5rpm.Afterwards
TiN sublayer and Ti sublayer successively alternating deposit in deposition process；It is one layer redeposited after to the last layer Ti sublayer deposition
TiN is as outermost layer.Matrix heating temperature is 300 DEG C ± 20 DEG C, and cathode targets are with Ti6Al4V titanium alloy substrate distance
22cm, Ti target purity are 99.99wt%, Ti target diameter 100mm, height 55mm.
As shown in Fig. 5 (a)-(b), morphology observation is carried out to deposited laminated coating, there are quantity for coating surface at most, ruler
Very little maximum molten drop, cross-section observation find that brilliant white is Ti sublayer, and dark gray is TiN sublayer, and there are larger-size molten for inside
Drip defect, part droplet size is more than TiN molecular layers thick, and laminated coating is well combined with Ti6Al4V matrix, do not find crack,
Lamination.It as shown in Fig. 6 (a)-(b), is found after 450 DEG C of corrosion 100h, surrosion is maximum, and weight gain adds in corrosion process
Fastly, it is peeled off after molten drops on surface is corroded, forms the etch pit being relatively large in diameter, Surface Creation r-TiO2Corrosion layer (Figure 10), in coating
Serious internal corrosion locally occurs for portion, and the oxide of protrusion is formed after molten drop corrosion, and the coating corrosion resistance is worst.
Embodiment 7
In the present embodiment, the metal/metal nitride laminated coating of high temperature resistant marine environment, by Ti sublayer and TiN
What sublayer alternating deposit was formed on Ti6Al4V matrix, be TiN layer close to matrix and top layer, each TiN molecular layers thick is
1.6 μm, each Ti molecular layers thick is 0.7 μm, and total number of plies is 15 layers.
The preparation method of the metal/metal nitride laminated coating of above-mentioned high temperature resistant marine environment, specifically include as
Lower step:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:4 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；So
Icon bombardment cleaning is carried out using ion plating equipment afterwards, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder, is put
Enter in ion plating vacuum chamber, close room door, being evacuated to vacuum degree is 1 × 10-2After Pa, it is passed through Ar, vacuum degree is maintained to exist
0.3Pa, it is 950V that matrix, which applies negative bias values, and duty ratio 50% carries out 5min icon bombardment cleaning to matrix.
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 2.0Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current in 600V, is set as 70A, starts the deposition of TiN sublayer, and 18min is accounted for
For sky than being set as 20%, specimen holder keeps rotation, and speed keeps 5rpm, Ti:N=1:1 (atomic ratio) in gained sublayer；Then it sinks
Product Ti sublayer, keeps Ti target current 70A constant, closes N2, it is passed through Ar, control pressure changes in 0.4Pa or so, substrate negative voltage value
For 50V, sedimentation time is controlled in 14min, and duty ratio is set as 20%, and specimen holder keeps the rotational velocity of 5rpm.Afterwards
TiN sublayer and Ti sublayer successively alternating deposit in deposition process；It is one layer redeposited after to the last layer Ti sublayer deposition
TiN is as outermost layer.Matrix heating temperature is 300 DEG C, and cathode targets and Ti6Al4V titanium alloy substrate distance are 21cm, Ti target
Purity is 99.99wt%, Ti target diameter 80mm, height 50mm.
Morphology observation, coating surface there are quantity more, larger-size molten drop, section are carried out to deposited laminated coating
Observation discovery brilliant white is Ti sublayer, and dark gray is TiN sublayer, and there are larger-size molten drop defect, part molten drop rulers for inside
Very little more than TiN molecular layers thick, laminated coating is well combined with Ti6Al4V matrix, does not find cracking, lamination.Through 450 DEG C of corruption
It is found after erosion 100h, surrosion increases, and increases weight and accelerates in corrosion process, and molten drops on surface peels off after being corroded, and forms etch pit, table
Face generates r-TiO2More serious internal corrosion, localized delamination after molten drop corrosion locally occur for corrosion layer, coat inside, which resists
Corrosivity is poor.
Comparative example
In this comparative example, TiN signal layer coating is prepared, is specifically comprised the following steps:
(1) cleaning of matrix
First by after the grinding of Ti6Al4V titanium alloy (Ti-6%Al-4%V, mass fraction) matrix, polishing treatment, it is put into third
In ketone and the solution of ethyl alcohol 1:2 mixing by volume, using 15~20kHz, 10~15min of ultrasonic cleaning, drying is taken out；So
Icon bombardment cleaning is carried out using ion plating equipment afterwards, the Ti6Al4V titanium alloy substrate handled well is suspended on specimen holder, is put
Enter in ion plating vacuum chamber, close room door, being evacuated to vacuum degree is 1 × 10-2After Pa, it is passed through Ar, vacuum degree is maintained to exist
0.3Pa, it is 1000V that matrix, which applies negative bias values, and duty ratio 60% carries out 3min icon bombardment cleaning to matrix.
(2) depositing TiN
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, maintain vacuum degree air pressure in 2.0Pa, matrix
The control of pulsed negative bias value opens cathode Ti target current, is set as 70A, sedimentation time 200min, duty ratio is set as in 600V
25%, specimen holder keeps rotation, and speed keeps 5rpm, Ti:N=1:1 (atomic ratio) in gained coating.
As shown in Fig. 7 (a)-(b), morphology observation is carried out to deposited laminated coating, there are uniform amounts for coating surface, melt
It is minimum to drip minimum number, size, cross-section observation finds that coat inside structure is uniform, fine and close, and coating is good in conjunction with Ti6Al4V matrix
It is good, cracking, lamination are not found.It as shown in Fig. 8 (a)-(b), is found after 450 DEG C of corrosion 100h, surrosion is minimum, rotten
Weight gain is most slow (Fig. 9) during erosion.It is uniform to corrode rear surface, does not find obviously to peel off, Surface Creation r-TiO2Corrosion layer (figure
10), coat inside does not locally find internal corrosion, which shows good corrosion resistance.
Claims (10)
1. a kind of metal-metal nitride laminated coating of high temperature resistant marine environment, which is characterized in that laminated coating is by Ti
What sublayer and TiN sublayer alternating deposit were formed on matrix, be TiN layer close to matrix and top layer.
2. the metal-metal nitride laminated coating of high temperature resistant marine environment as described in claim 1, feature exist
In each TiN molecular layers thick is 1.7~2.0 μm, and each Ti molecular layers thick is 0.1~1.0 μm, metal/metal nitride multilayer
Total number of plies of coating is the odd number in 13~21 layers.
3. the metal-metal nitride laminated coating of high temperature resistant marine environment as described in claim 1, feature exist
In matrix Ti6Al4V.
4. the metal-metal nitride laminated coating of high temperature resistant marine environment described in a kind of one of claims 1 to 3
Preparation method, which is characterized in that specifically include that steps are as follows:
(1) matrix cleans
After the grinding of Ti6Al4V titanium alloy substrate, polishing treatment, it is put into acetone and the ethyl alcohol mixed solution in 1:2~4 by volume
In, using 15~20kHz, 10~15min of ultrasonic cleaning, take out drying；The sample handled well is suspended on specimen holder, is put
Enter in ion plating vacuum chamber, close room door, carries out icon bombardment cleaning using ion plating equipment；
(2) alternating deposit TiN sublayer and Ti sublayer
After step (1) icon bombardment cleaning, Ar is cut off, N is passed through2, Ti6Al4V titanium alloy substrate application pulsed negative bias,
Cathode Ti target current is opened, the deposition of TiN sublayer is started；Then depositing Ti sublayer keeps Ti target current constant, closes N2, lead to
Enter Ar, adjust Ti6Al4V titanium alloy substrate negative bias values, carries out Ti sublayer deposition；In later deposition process TiN sublayer and
Ti sublayer successively alternating deposit；After to the last layer Ti sublayer deposition, one layer of TiN is as outermost layer for redeposition.
5. the preparation method of the metal-metal nitride laminated coating of high temperature resistant marine environment as claimed in claim 4,
It is characterized in that, before icon bombardment cleaning, being evacuated to vacuum degree is 7 × 10 in step (1)-3~10 × 10-3Pa is passed through Ar
Maintain vacuum degree in 0.2~0.5Pa, it is 850~950V that Ti6Al4V titanium alloy substrate, which applies negative bias values, duty ratio is 30~
60%, the icon bombardment cleaning time is 3~10min.
6. the preparation method of the metal-metal nitride laminated coating of high temperature resistant marine environment as claimed in claim 4,
It is characterized in that, Ti target purity is 99.99wt% or more in step (2), it is highly 50~60mm that diameter, which is 80~120mm,
The bulk purity of argon gas and nitrogen is 99.99% or more.
7. the preparation method of the metal-metal nitride laminated coating of high temperature resistant marine environment as claimed in claim 4,
It is characterized in that, in step (2), TiN sublayer deposition parameter are as follows: Ti target current 60~80A, N2Pressure is 1.4~2.0Pa, is born
Bias value is 550~600V, and sedimentation time is 18~21min, and duty ratio is that Ti and N atomic ratio is in 20~30%, TiN sublayer
1:1。
8. the preparation method of the metal-metal nitride laminated coating of high temperature resistant marine environment as claimed in claim 4,
It is characterized in that, in step (2), Ti sublayer deposition parameter are as follows: Ti target current 60~80A, Ar pressure is 0.2~0.5Pa, negative bias
Pressure value is 50~100V, and sedimentation time is 2~21min, and duty ratio is 20~30%.
9. the preparation method of the metal-metal nitride laminated coating of high temperature resistant marine environment as claimed in claim 4,
It is characterized in that, Ti target and Ti6Al4V titanium alloy substrate distance are 17~22cm, sample in step (1) to (2) deposition process
Frame is with 3~6rpm speed rotation.
10. the preparation side of the metal-metal nitride laminated coating of high temperature resistant marine environment as claimed in claim 4
Method, which is characterized in that in coating deposition process, the titanium alloy-based temperature of Ti6Al4V is 300 DEG C ± 20 DEG C.
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