CN109913796A - TiAlN composite coating on surface of titanium alloy and preparation method thereof - Google Patents
TiAlN composite coating on surface of titanium alloy and preparation method thereof Download PDFInfo
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- CN109913796A CN109913796A CN201910285352.9A CN201910285352A CN109913796A CN 109913796 A CN109913796 A CN 109913796A CN 201910285352 A CN201910285352 A CN 201910285352A CN 109913796 A CN109913796 A CN 109913796A
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- 238000000576 coating method Methods 0.000 title claims abstract description 118
- 239000011248 coating agent Substances 0.000 title claims abstract description 114
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 229910010037 TiAlN Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000005121 nitriding Methods 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 32
- 239000010936 titanium Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003961 penetration enhancing agent Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000007767 bonding agent Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 229910010038 TiAl Inorganic materials 0.000 claims description 6
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 230000008595 infiltration Effects 0.000 abstract description 8
- 238000001764 infiltration Methods 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000010849 ion bombardment Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 230000008569 process Effects 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 9
- 230000007704 transition Effects 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021330 Ti3Al Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
The invention discloses a TiAlN composite coating on the surface of a titanium alloy and a preparation method thereof, wherein a titanium alloy matrix is pretreated, and then is embedded in an embedding infiltration agent and is aluminized to obtain an aluminized layer; and (3) placing the aluminized layer in a double-glow ion nitriding furnace, and performing ion bombardment cleaning and nitriding treatment to obtain the TiAlN composite coating on the surface of the titanium alloy. According to the invention, the embedded aluminized layer is subjected to ion bombardment cleaning and ion nitriding treatment, and the TiAlN composite coating is generated in situ, so that the aluminized layer is metallurgically bonded with the titanium alloy substrate, and the bonding force between the titanium alloy substrate and the surface modified coating is greatly improved; meanwhile, the high-stress contact state caused by the difference of the thermal expansion coefficient, the hardness and the elastic modulus between the TiAlN coating with high hardness and high rigidity and the titanium alloy substrate can be effectively relieved, and the service life of the coating is prolonged.
Description
Technical field
The present invention relates to the TiAlN composite coating of technical field of surface coating more particularly to a kind of titanium alloy surface and its
Preparation method.
Background technique
Nitride coatings have excellent wear-resisting property, anti-erosion property, wide in aviation field and field of machining
The general surface applied to alloy is modified.TiAlN is a kind of excellent hard films, has good wearability and erosion wear resistance,
Aviation and field of machining all have broad application prospect.
Currently, most TiAlN coatings mostly uses thermal spraying, magnetron sputtering or multi sphere ion plating technology to prepare, and thermal jet
The bond strength of the coating and matrix that apply preparation is lower；Magnetron sputtering multi sphere ion plating technology is unfavorable in complex contour, blocks
Serious parts surface carries out coating preparation, and the coating of magnetron sputtering preparation is relatively thin, is not suitable for when coating thickness requirement is high, and
Coating preparation cost is too high；Multi sphere ion plating technology is easy to form big drop defect in coat inside, influences end-use properties.
Therefore, more efficient, thicker, the stronger TiAlN coating of binding force is developed, is urgent problem to be solved in nitride coatings research.
Summary of the invention
Aiming at the problems existing in the prior art, it is multiple that the purpose of the present invention is to provide a kind of TiAlN of titanium alloy surface
Coating and preparation method thereof is closed, the present invention carries out icon bombardment cleaning to pack cementation aluminium layer and glow discharge nitriding is handled, in-situ preparation
TiAlN composite coating makes infiltration layer and titanium alloy substrate metallurgical bonding, substantially increases titanium alloy substrate and surface modified coat
Binding force；Meanwhile, it is capable to be effectively relieved the thermal expansion coefficient between the TiAlN coating and titanium alloy substrate of high rigidity, high rigidity,
Hardness and the difference of elasticity modulus and the high stress contact condition generated extend coating service life.
In order to achieve the above objectives, the present invention is resolved using following technical scheme.
(1) the TiAlN composite coating of a kind of titanium alloy surface, including aluminized coating and Ti1-xAlxN layers, wherein 0.25≤x
≤0.5。
Preferably, the aluminized coating is Ti3One of Al or TiAl or a variety of.
Preferably, the aluminized coating with a thickness of 6-15 μm, the Ti1-xAlxN layers with a thickness of 4-10 μm.
(2) the TiAlN composite coating and preparation method thereof of a kind of titanium alloy surface, comprising the following steps:
Step 1, crude product titanium alloy substrate is pre-processed, obtains titanium alloy substrate；Titanium alloy substrate is placed in pack cementation
It is embedded in agent, obtains embedding matrix, embedding matrix is placed in progress aluminising processing in atmosphere furnace, obtains aluminized coating；
Step 2, aluminising is placed in double brightness ion-nitriding furnaces, first carries out icon bombardment cleaning, then carry out Nitrizing Treatment,
Obtain the TiAlN composite coating of titanium alloy surface.
Preferably, in step 1, the pretreatment is successively to use 120 mesh, 240 mesh, 400 mesh to crude product titanium alloy substrate
It polishes with 800 mesh abrasive paper for metallograph, is cleaned by ultrasonic 20min, rinse 3-5min, drying；
It is further preferred that the temperature of the drying is 70-80 DEG C, the time of drying is 2-3h；
Preferably, in step 1, the embedding penetration enhancer includes: aluminium powder, fluoride powder and alumina powder.
Preferably, in step 1, the material quality accounting of the embedding penetration enhancer are as follows: aluminium powder 10%, fluoride powder 1-3% are remaining
Amount is alumina powder.
It is further preferred that the fluoride powder is fluorination sodium powder or ammonium fluoride powder.
Preferably, in step 1, it is described embedding penetration enhancer the preparation method comprises the following steps: by aluminium powder, fluoride powder and alumina powder carry out
Rolling ball milling to get.
It is further preferred that the revolving speed of the rolling ball milling is 10r/min, the time 3-4h of rolling ball milling.
Preferably, the embedding is sealed for titanium alloy substrate embedment to be equipped in the container of embedding penetration enhancer using bonding agent
Container.
Preferably, the bonding agent is mixed to prepare by silica solution and schmigel 1:5 in mass ratio.
It is further preferred that the silica content of the silica solution is 20%.
Preferably, in step 1, the pressure of the aluminising processing is not less than 5 × 103Pa, the rate of heat addition are 6 DEG C/min, temperature
Degree is 700-900 DEG C, time 2-5h.
Preferably, in step 2, the gas source of the icon bombardment cleaning is argon gas, and pressure is not less than 20Pa, and ion bombardment is clear
The electric current washed is 1-1.5A, and temperature is 500-600 DEG C, time 30-60min.
Preferably, in step 2, the nitrogen source gas flow of the Nitrizing Treatment is 0.10-0.26L/min, Nitrizing Treatment
Glow ion electric current is 1.5-2A, and 700-900 DEG C of the temperature of Nitrizing Treatment, the time of Nitrizing Treatment is 1-2h.
Compared with prior art, the invention has the benefit that
(1) present invention carries out icon bombardment cleaning to pack cementation aluminium layer and glow discharge nitriding is handled, and in-situ preparation TiAlN is compound
Coating makes infiltration layer and titanium alloy substrate metallurgical bonding, substantially increases the binding force of titanium alloy substrate and surface modified coat.
(2) present invention adjusts the Al content in infiltration layer by changing the content of each component in embedding penetration enhancer, obtains respectively
With Ti3Aluminized coating based on Al or TiAl, to obtain the Ti with expected Al content1-xAlxN coating；Meanwhile passing through aluminized coating
The thermal expansion system between the TiAlN composite coating and titanium alloy substrate of high rigidity, high rigidity can be effectively relieved as transition zone
Number, hardness and elasticity modulus difference and the high stress contact condition that generates, extend coating service life.
(3) not needing target in the present invention can be obtained TiAlN composite coating, avoid traditional physical vapour deposition (PVD)
(PVD) quality of method prepares coating is by the targets such as target purity, density and institutional framework index and magnetic field, electric field and temperature etc.
The TiAlN composite coating of the combined influence of preparation technology of coating parameter, preparation is stable and controllable for quality, and pack cementation coupled ion seeps
Mode it is at low cost, easy to operate, high-efficient, have a clear superiority for the surface modification treatment of complex component.
Detailed description of the invention
Fig. 1 is the surface scan photo of TiAlN composite coating prepared by the embodiment of the present invention 1.
Fig. 2 is the surface XRD spectrum of TiAlN composite coating prepared by the embodiment of the present invention 1.
Fig. 3 is the cross section structure schematic diagram of TiAlN composite coating prepared by the embodiment of the present invention 1.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the invention.
In order to further illustrate the present invention, with reference to embodiments to a kind of titanium alloy surface provided by the invention
TiAlN composite coating and preparation method thereof is described in detail.
Embodiment 1
A kind of preparation method of the TiAlN composite coating of titanium alloy surface, comprising the following steps:
Step 1, by crude product titanium alloy TC 4 plate successively use the carborundum paper of 120 mesh, 240 mesh, 400 mesh and 800 mesh into
Then titanium alloy after grinding process is placed in progress ultrasonic cleaning 20min in ultrasonic washing instrument, later by row grinding process
After being rinsed using flowing water, 70 DEG C of drying 3h obtain titanium alloy substrate.
4g aluminium powder, 0.4g fluorination sodium powder and 35.6g alumina powder are subjected to rolling ball milling 4h, rolling ball milling revolving speed 10r/
Min is to get embedding penetration enhancer；Silica solution 3g and schmigel 15g that silica content is 20wt% are mixed to prepare bonding agent；By titanium
In crucible of the alloy substrate embedment equipped with embedding penetration enhancer, crucible is covered, and using between bonding agent sealed crucible and crucible cover
Gap obtains embedding matrix.
Embedding matrix is placed in atmosphere furnace, firstly, to atmosphere furnace vacuumize process, until the vacuum in furnace is 4 × 10- 2Then Pa is passed through argon gas into furnace, until the air pressure in furnace is 6 × 103Pa, then with the rate of heat addition of 6 DEG C/min, by atmosphere furnace
900 DEG C are heated to, keeps the temperature 3.5h at 900 DEG C, aluminising processing is carried out to embedding matrix, last furnace cooling obtains crude product aluminising
The surface of crude product aluminized coating is slightly polished using 1500 mesh sand paper, removes the penetration enhancer sticked, obtain aluminized coating by layer.
Step 2, aluminising is placed in double brightness ion-nitriding furnaces, firstly, double brightness ion-nitriding furnaces are vacuumized, until
Pressure in furnace is 8Pa, then argon gas is passed through into furnace, until the pressure in furnace is 30Pa, carries out icon bombardment cleaning to aluminized coating,
The electric current of icon bombardment cleaning is 1.5A, and temperature is 550 DEG C, time 45min；Then, it is passed through nitrogen in Xiang Shuanhui ion furnace,
The flow of nitrogen is 0.20L/min, and the electric current of glow discharge nitriding is 1.7A, double brightness ion-nitriding furnaces is warming up to 900 DEG C, 900
1h is kept the temperature at DEG C, and Nitrizing Treatment is carried out to the aluminized coating of titanium alloy surface, obtains the TiAlN composite coating of titanium alloy surface.Institute
The transition zone for obtaining composite coating is Ti3Al layers, surface Ti1-xAlxN nitride layer.According to the scanning electron microscopic observation of coating cross sections
Pattern and the ingredient of energy spectrum analysis determine the different layer thickness of composite coating, the overall thickness of coating is about 15 μm, upper layer
Ti1-xAlxN section thickness is about 5 μm.
Embodiment 2
A kind of preparation method of the TiAlN composite coating of titanium alloy surface, comprising the following steps:
Step 1, by crude product titanium alloy TC 4 plate using successively using 120 mesh, 240 mesh, 400 mesh and 800 mesh carborundum papers
Grinding process is carried out, the titanium alloy after grinding process is then placed in progress ultrasonic cleaning 25min in ultrasonic washing instrument, it
Flowing water rinses 80 DEG C of drying after 5min afterwards, obtains titanium alloy substrate.
4g aluminium powder, 0.48g ammonium fluoride powder and 35.52g alumina powder are subjected to rolling ball milling 4h, rolling ball milling revolving speed 10r/
Min is to get embedding penetration enhancer；Silica solution 4g and schmigel 20g that silica content is 20wt% are mixed to prepare bonding agent；By titanium
In crucible of the alloy substrate embedment equipped with embedding penetration enhancer, crucible is covered, and using between bonding agent sealed crucible and crucible cover
Gap obtains embedding matrix.
Embedding matrix is placed in atmosphere furnace, firstly, to atmosphere furnace vacuumize process, until the vacuum in furnace is 5 × 10- 2Then Pa is passed through argon gas into furnace, until the air pressure in furnace is 6 × 103Pa, then with the rate of heat addition of 6 DEG C/min, by atmosphere furnace
850 DEG C are heated to, keeps the temperature 4.5h at 850 DEG C, aluminising processing is carried out to embedding matrix, last furnace cooling obtains crude product aluminising
The surface of crude product aluminized coating is slightly polished using 1500 mesh sand paper, removes the penetration enhancer sticked, obtain the aluminising of titanium alloy surface by layer
Layer.
Step 2, the aluminising of titanium alloy surface is placed in double brightness ion-nitriding furnaces, firstly, to double brightness ion-nitriding furnaces
It is vacuumized, until the pressure in furnace is 6Pa, then is passed through argon gas into furnace, until the pressure in furnace is 35Pa, to titanium alloy surface
Aluminized coating carry out icon bombardment cleaning, the electric current of icon bombardment cleaning is 1.2A, and temperature is 500 DEG C, time 40min；So
Afterwards, be passed through nitrogen in Xiang Shuanhui ion furnace, the flow of nitrogen is 0.20L/min, and the electric current of glow discharge nitriding is 1.5A, by double brightness from
Sub- nitriding furnace is warming up to 850 DEG C, keeps the temperature 1.5h at 850 DEG C, carries out Nitrizing Treatment to the aluminized coating of titanium alloy surface, obtains titanium
The TiAlN composite coating of alloy surface.The transition zone of gained composite coating is TiAl infiltration layer, superficial layer Ti1-xAlxN nitride
Layer.The different layer thickness of composite coating is determined according to the pattern of composite coating scanning electron microscopic observation and the ingredient of energy spectrum analysis,
The overall thickness of coating is about 8 μm, upper layer Ti1-xAlxN section thickness is about 4 μm.
Embodiment 3
A kind of preparation method of the TiAlN composite coating of titanium alloy surface, comprising the following steps:
Step 1, by crude product titanium alloy TC 4 plate using successively using 120 mesh, 240 mesh, 400 mesh and 800 mesh carborundum papers
Grinding process is carried out, the titanium alloy after grinding process is then placed in progress ultrasonic cleaning 30min in ultrasonic washing instrument, it
Flowing water rinses 75 DEG C of drying after 5min afterwards, obtains titanium alloy substrate.
4g aluminium powder, 0.56g ammonium fluoride powder and 35.44g alumina powder are subjected to rolling ball milling 4h, rolling ball milling revolving speed 10r/
Min is to get embedding penetration enhancer；Silica solution 4g and schmigel 20g that silica content is 20wt% are mixed to prepare bonding agent；By titanium
In crucible of the alloy substrate embedment equipped with embedding penetration enhancer, crucible is covered, and using between bonding agent sealed crucible and crucible cover
Gap obtains embedding matrix.
Embedding matrix is placed in atmosphere furnace, firstly, to atmosphere furnace vacuumize process, until the vacuum in furnace is 3 × 10- 2Then Pa is passed through argon gas into furnace, until the air pressure in furnace is 6 × 103Pa, then with the rate of heat addition of 6 DEG C/min, by atmosphere furnace
800 DEG C are heated to, keeps the temperature 4h at 800 DEG C, aluminising processing is carried out to embedding matrix, last furnace cooling obtains crude product aluminized coating,
The surface of crude product aluminized coating is slightly polished using 1500 mesh sand paper, the penetration enhancer sticked is removed, obtains the aluminized coating of titanium alloy surface.
Step 2, the aluminising of titanium alloy surface is placed in double brightness ion-nitriding furnaces, firstly, to double brightness ion-nitriding furnaces
It is vacuumized, until the pressure in furnace is 6Pa, then is passed through argon gas into furnace, until the pressure in furnace is 30Pa, to titanium alloy surface
Aluminized coating carry out icon bombardment cleaning icon bombardment cleaning electric current be 1.0A, temperature be 500 DEG C, time 55min；So
Afterwards, be passed through nitrogen in Xiang Shuanhui ion furnace, the flow of nitrogen is 0.20L/min, and the electric current of glow discharge nitriding is 2.0A, by double brightness from
Sub- nitriding furnace is warming up to 750 DEG C, keeps the temperature 2h at 750 DEG C, carries out Nitrizing Treatment to the aluminized coating of titanium alloy surface, obtains titanium conjunction
The TiAlN composite coating of gold surface.The transition zone of gained composite coating is TiAl layers, superficial layer Ti1-xAlxN nitride layer.
The different layer thickness of composite coating, coating are determined according to the pattern of composite coating scanning electron microscopic observation and the ingredient of energy spectrum analysis
Overall thickness be about 14 μm, upper layer Ti1-xAlxN section thickness is about 7 μm.
Electronic Speculum and X-ray diffraction interpretation of result are scanned to the resulting TiAlN composite coating of the embodiment of the present invention 1, joined
The surface topography photo that Fig. 1 is coating is examined, Fig. 2 is the X-ray diffraction material phase analysis of coating as a result, it will be seen from figure 1 that this hair
Composite coating structure prepared by bright embodiment 1 is fine and close, uniform；Figure it is seen that compound painting prepared by the embodiment of the present invention 1
The main object of layer is mutually Ti3Al and TiAlN, wherein the diffracted signal of Ti phase comes from titanium alloy substrate；TiAlN phase indicates compound
The Ti on coating top1-xAlxN layers of phase, due to Ti1-xAlxN is actually the part Ti atom in Al atom substitution TiN lattice,
And when the Al content in lattice is less than Ti content, Ti1-xAlxN still keeps B1 structure (the i.e. face-centered cubic crystalline substance of typical TiN
Lattice structure), thus carry out Ti1-xAlxThe map of standard TiN is still used when N layers of XRD analysis, a small amount of offset of the angle of diffraction indicates
The lattice constant due to caused by the effect of Al element changes, in addition Ti1-xAlxN layers are relatively thin, therefore, general XRD analysis TiAlN
To indicate Ti1-xAlxN phase indicates to be dissolved Al atom in TiN.Fig. 3 is the structural representation of 1 products obtained therefrom of the embodiment of the present invention
Figure, 1 products obtained therefrom of the embodiment of the present invention is followed successively by titanium matrix TC4, transition zone Ti from inside to outside as we know from the figure3Al and table
Surface layer Ti1-xAlxN。
It can be seen that the work that the method for the present invention can be handled by adjusting embedding penetration enhancer proportion with aluminising from embodiment 1-3
The transition zone of skill gain of parameter difference main component is obtained with Ti3Aluminized coating based on Al or TiAl, to be had
It is expected that the Ti of Al content1-xAlxN coating；Meanwhile high rigidity, high rigidity can be effectively relieved as transition zone by aluminized coating
The difference of thermal expansion coefficient, hardness and elasticity modulus between TiAlN composite coating and titanium alloy substrate and the height generated is answered
Power contact condition extends coating service life.
It can be seen that the overall thickness of the TiAlN composite coating of titanium alloy surface prepared by the method for the present invention from embodiment 1-3
It is micron level, while transition in gained composite coating can be adjusted by the technological parameter of aluminising processing and Nitrizing Treatment
Relative thickness between layer and superficial layer makes thermal expansion coefficient between titanium alloy substrate and the composite coating on its surface, hardness
It is preferably matched with elasticity modulus, and then reduces the stress between titanium alloy substrate and composite coating, obtain better coating power
Performance is learned, coating service life is extended.
The TiAlN composite coating for tens micron thickness that the method for the present invention obtains is in coating as wearing layer or etch resistant layer
When, it is remarkably improved the performance and used life of coating, is had broad application prospects in aviation and machining field.Simultaneously originally
It is the metallurgical bonding by high-temperature process between the big thickness coatings and matrix of invention, binding force is very strong, compared to current
The technologies such as PVD, thermal spraying, multi-arc ion coating, the binding force solved between the matrix and coating when coating layer thickness is big is low, applies
The caducous problem of layer；The method of the present invention preparation process is not necessarily to expensive target, only needs the powder penetrating agent of low cost and anti-
It answers gas can be obtained, greatly reduces the production cost of TiAlN composite coating.
The present invention is by preparing TiAlN composite coating in aluminising layer surface, i.e., clear to pack cementation aluminium layer progress ion bombardment
It washes and is handled with glow discharge nitriding, in-situ preparation TiAlN composite coating, matrix is strong with coating binding force.Wherein, the method for pack cementation into
Row chemical vapor deposition prepares coating, it is at low cost, do not influenced by workpiece size and geometry.During pack cementation aluminium powder with
Activator fluoride reacts at a certain temperature generates gaseous halide, is then generated and is lived by displacement, decomposition and disproportionation
Property Al atom, active Al atom adsorbs in metal base surface, absorbs and gradually diffuse to metal inside, thus infiltration layer and base
Body metallurgical bonding, and fatigue behaviour of the residual compressive stress to improve material, the thickness convenient for controlling infiltration layer can be introduced.After pack cementation
Nitrogen or ammonia etc. are filled with as double brightness ions and seeps working gas, then nitration case is formed in layer surface, nitration case and infiltration layer
The diffusion layer in metallurgical bonding is formed, coating is not easy to peel off.Based on the above analysis it may be speculated that changing gas in nitriding process
Partial pressure, the coating that metallic atom and nitrogen-atoms have gradient distribution may be obtained.
Reagent used in the present invention is commercially available, method used in the present invention, if being conventional side without specified otherwise
Method.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
It encloses.
Claims (10)
1. a kind of TiAlN composite coating of titanium alloy surface, which is characterized in that including what is successively grown on titanium alloy substrate surface
Aluminized coating and Ti1-xAlxN layers, wherein 0.25≤x≤0.5；The object of the aluminized coating is mutually Ti3One of Al or TiAl or more
Kind.
2. the TiAlN composite coating of titanium alloy surface according to claim 1, which is characterized in that the thickness of the aluminized coating
Degree be 6-15 μm, the surface layer TiAlN with a thickness of 4-10 μm.
3. a kind of preparation method of the TiAlN composite coating of titanium alloy surface, which comprises the following steps:
Step 1, crude product titanium alloy substrate is pre-processed, obtains titanium alloy substrate；Titanium alloy substrate is placed in embedding penetration enhancer
It is embedded, obtains embedding matrix, embedding matrix is placed in progress aluminising processing in atmosphere furnace, obtains aluminized coating；
Step 2, aluminising is placed in double brightness ion-nitriding furnaces, first carries out icon bombardment cleaning, then carry out Nitrizing Treatment, obtains
The TiAlN composite coating of titanium alloy surface.
4. the preparation method of the TiAlN composite coating of titanium alloy surface according to claim 3, which is characterized in that step 1
In, the embedding penetration enhancer includes aluminium powder, fluoride powder and alumina powder；Wherein, the fluoride powder is fluorination sodium powder or fluorination
Ammonium powder.
5. the preparation method of the TiAlN composite coating of titanium alloy surface according to claim 4, which is characterized in that step 1
In, the material quality accounting of the embedding penetration enhancer are as follows: aluminium powder 10%, fluoride powder 1-3%, surplus are alumina powder.
6. the preparation method of the TiAlN composite coating of titanium alloy surface according to claim 3, which is characterized in that described
Titanium alloy substrate embedment is is equipped in the container of embedding penetration enhancer by embedding, using bonding agent sealing container.
7. the preparation method of the TiAlN composite coating of titanium alloy surface according to claim 6, which is characterized in that described
Bonding agent is mixed to prepare by silica solution and schmigel in mass ratio 1: 5.
8. the preparation method of the TiAlN composite coating of titanium alloy surface according to claim 3, which is characterized in that step 1
In, the pressure of the aluminising processing is not less than 5 × 103Pa, the rate of heat addition of aluminising processing are 6 DEG C/min, the temperature of aluminising processing
Degree is 700-900 DEG C, and the time of aluminising processing is 2-5h.
9. the preparation method of the TiAlN composite coating of titanium alloy surface according to claim 3, which is characterized in that step 2
In, the gas source of the icon bombardment cleaning is argon gas, and the pressure of icon bombardment cleaning is not less than 20Pa, the electricity of icon bombardment cleaning
Stream is 1-1.5A, and the temperature of icon bombardment cleaning is 500-600 DEG C, and the time of icon bombardment cleaning is 30-60min.
10. the preparation method of the TiAlN composite coating of titanium alloy surface according to claim 3, which is characterized in that step
In 2, the nitrogen source gas flow of the Nitrizing Treatment is 0.10-0.26L/min, and the glow ion electric current of Nitrizing Treatment is 1.5-
2A, 700-900 DEG C of the temperature of Nitrizing Treatment, the time of Nitrizing Treatment are 1-2h.
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| CN117587357B (en) * | 2024-01-19 | 2024-04-09 | 北京开元新能科技有限公司 | Metal bipolar plate for proton exchange membrane fuel cell and preparation method and application thereof |
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