CN106493348B - A kind of TiAl3/ Al2O3Composite powder and its preparation method and application - Google Patents
A kind of TiAl3/ Al2O3Composite powder and its preparation method and application Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 67
- 229910010039 TiAl3 Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 238000000576 coating method Methods 0.000 claims abstract description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 48
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 48
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 229910010038 TiAl Inorganic materials 0.000 claims abstract description 15
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 10
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 239000008199 coating composition Substances 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 238000009792 diffusion process Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 23
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 3
- 239000011253 protective coating Substances 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 238000010288 cold spraying Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- 229910000951 Aluminide Inorganic materials 0.000 description 5
- 229910006281 γ-TiAl Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910004349 Ti-Al Inorganic materials 0.000 description 2
- 229910021330 Ti3Al Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910004692 Ti—Al Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003778 catagen phase Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013034 coating degradation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000007667 floating Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
Landscapes
- Coating By Spraying Or Casting (AREA)
- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention relates to titanium alloy high-temperature protective coating technology of preparing, specially a kind of TiAl3/Al2O3Composite powder and its preparation method and application.Pure Al and nano-TiO are selected first2Powder is heat-treated with certain proportion high-energy ball milling and TiAl is made after a certain period of time3/Al2O3Composite powder, then composite powder obtained is sprayed on titanium alloy base material and forms TiAl under conditions of 100~700 DEG C of temperature, 0.3~5.0MPa of pressure with the method for cold air power spraying and coating3/Al2O3Composite coating.Coating composition is TiAl3And Al2O3, wherein Al2O3It is evenly distributed in the coating, coating layer thickness is at 10 μm or more.Preparation method of the present invention is easy to operate, easy control of components, and obtained coating porosity is low, it is good with matrix compatibility, binding force, with preferable high temperature oxidation resistance, the counterdiffusion of coating and matrix can be substantially reduced, titanium alloy high-temperature problem of oxidation can be well solved.
Description
Technical field：
The present invention relates to titanium alloy high-temperature protective coating technology of preparing, specially a kind of TiAl3/Al2O3Composite powder and its
Preparation method and application.
Background technology：
Ti-Al systems alloy, especially α-Ti3Al, γ-TiAl and O phases Ti2AlNb alloys have low-density, high intensity, height
Fusing point and excellent creep-resistant property can be widely used for automobile or the high-temperature component of aero-engine, be very promising
Light-duty high-temperature material.See document [1] H.Clemens, and H.Kestler, Processing and Applications of
Intermetallicγ‐TiAl‐Based Alloys,Adv.Eng.Mater.,2000,2(9), p 551-570.However Ti-
Al alloys high temperature oxidation resistance is insufficient, and especially when its temperature in use is more than 800 DEG C, surface, which is formed, does not have protectiveness
TiO2Oxidation film, while oxygen can penetrate into matrix and form solid solution with Titanium base, drop low-alloyed plasticity, seriously affect conjunction
The performance of gold.See document [2] A.Rahmel, M.Sch ü tze, and W.Quadakkers, Fundamentals of
TiAl Oxidation–a Critical Review, Mater.Corros.,1995,46(5),p 271-285.Therefore, titanium
Alloy is protected under high-temperature situation using must apply coating.
Currently, there are many kinds of the protective coatings of Ti-Al alloys.Wherein, coat of aluminide has well with matrix alloy
Compatibility, obtains extensive research, and traditional method for preparing coat of aluminide mainly has：Pack aluminizing, hot-dip
Aluminising, Electroplating Aluminum and thermal diffusion, sputtered aluminum and thermal diffusion and thermal spraying aluminum and thermal diffusion, the calorize formed using these methods
Object coating is all the aluminium and matrix reaction generation by inwardly spreading.Although these coat of aluminide improve to a certain extent
The antioxygenic property of matrix, but it still remains deficiency, and one side coating brittleness is higher, is also easy to produce crackle；On the other hand it is high
Warm oxidation process floating coat causes coating degradation speed fast with matrix counterdiffusion, sees document [3-9]：
[3]C.H.Koo,and T.H.Yu,Pack Cementation Coatings on Ti3Al-Nb Alloys to
Modify the High-Temperature Oxidation Properties,Surf.Coat.Technol.,2000, 126
(2-3),p 171-180；
[4]Z.D.Xiang,S.Rose,and P.K.Datta,Pack Deposition of Coherent
Aluminide Coatings on Gamma-TiAl for Enhancing Its High Temperature Oxidation
Resistance, Surf.Coat.Technol.,2002,161(2-3),p 286-292；
[5]V.Gauthier,F.Dettenwanger,M.Schütze,V.Shemet,and W.Quadakkers,
Oxidation-Resistant Aluminide Coatings on γ-TiAl,Oxid.Met.,2003,59(3-4),p
233-255；
[6]T.Sasaki,T.Yagi,T.Watanabe,and A.Yanagisawa,Aluminizing of TiAl-
Based Alloy Using Thermal Spray Coating,Surf.Coat.Technol.,2011,205(13-14),p
3900-3904；
[7]M.S.Chu,and S.K.Wu,The Improvement of High Temperature Oxidation
of Ti–50Al by Sputtering Al Film and Subsequent Interdiffusion Treatment,Acta
Mater., 2003,51(11),p 3109-3120；
[8]F.A.Varlese,M.Tului,S.Sabbadini,F.Pellissero,M.Sebastiani,and E.
Bemporad,Optimized Coating Procedure for the Protection of TiAl Intermetallic
Alloy against High Temperature Oxidation,Intermetallics,2013,37,p 76-82；
[9]M.Miyake,S.Tajikara,and T.Hirato,Fabrication of TiAl3Coating on
TiAl-Based Alloy by Al Electrodeposition from Dimethylsulfone Bath and
Subsequent Annealing,Surf.Coat.Technol.,2011,205(21-22),p 5141-5146。
Therefore, how to solve the problems, such as in coat of aluminide that above-mentioned two are the passes for further increasing coating performance
Key.TiAl3/Al2O3There are a large amount of inert Al in composite coating2O3, can as the diffusion barrier between coating and matrix, from
And reduce the catagen speed of coating at high temperature；In addition composite coating is made of particle, with traditional coat of aluminide group
Knit difference, this resistance to crack extension ability for organizing that coating can be improved to a certain extent.
Invention content
The purpose of the present invention is to provide a kind of TiAl for titanium alloy high-temperature protection3/Al2O3Composite powder and its system
Preparation Method and application solve α-Ti3Al, γ-TiAl and O phases Ti2The high-temperature oxydation problem of AlNb alloys.The composite powder and painting
Composition of layer is TiAl3And Al2O3, there is preferable resistance to high temperature oxidation and environmental embrittlement performance, preparation method to use cold spraying, behaviour
Make easy, easily controllable, formation coating quality height.
The technical scheme is that：
A kind of TiAl3/Al2O3Composite powder, composite powder ingredient are TiAl3And Al2O3, grain size is 10~80 μm, and
Al2O3It is uniformly distributed in composite powder.
The TiAl3/Al2O3The preparation method of composite powder selects pure Al and nano-TiO2Powder is with mass ratio 3:1
~1:High-energy ball milling mixes 1~4h between 1, and mixed powder is in 300~800 DEG C of 2~20h of heat diffusion treatment, furnace cooling
After generate TiAl3/Al2O3Composite powder.
The TiAl3/Al2O3Prepared TiAl is selected in the application of composite powder3/Al2O3Composite powder, use are cold
Aerodynamic force spraying technology, operating condition are 100~700 DEG C of temperature, and 0.3~5.0MPa of pressure is sprayed directly into titanium alloy substrate
Upper formation composite coating.
The TiAl3/Al2O3The application of composite powder, Al2O3It is uniformly distributed in composite coating.
The TiAl3/Al2O3Mechanical snap is presented with matrix in the application of composite powder, composite coating, and binding force is good.
The TiAl3/Al2O3The application of composite powder, composite coating composition is identical as composite powder ingredient, applies thickness
Degree is at 10 μm or more.
The present invention design philosophy be：
Cold spraying is an emerging coat preparing technology developed in recent years, and different from traditional thermal spraying, it is
Under low-temperature condition, plastic deformation when by high velocity powder particles hit matrix is formed by coating, therefore cold spraying is special
It is suitble to the preparation of the powder and basal body coating layer to heat and oxidation-sensitive.Present invention high-energy ball milling Al/TiO2Mixed-powder and heat
Processing prepares TiAl3/Al2O3Composite powder, the then TiAl prepared by direct cold spraying3/Al2O3Composite powder is formed
TiAl3/Al2O3Composite coating.This method is easy to operate, easily controllable, and high-temperature oxydation experiment shows that the coating has and resists well
Oxidation susceptibility, the technology are not reported at home and abroad.
Advantages of the present invention and advantageous effect are：
1. composite powder and coating prepared by the present invention, the high temperature protection to titanium alloy include high-temperature oxydation and environmental embrittlement
It is largely effective.
2. composite powder of the present invention is made using high-energy ball milling mixed-powder and its heat treatment method, prepared composite powder
Last two-phase is evenly distributed, easy control of components.
3. composite coating is prepared using cold spraying method.Non-oxidation in spraying process, without phase-change, coating composition and composite powder
End is consistent, and operating process is simple.
4. the present invention uses cold spraying method prepares coating, matrix alloy is not influenced.
Description of the drawings
Fig. 1 is the TiAl prepared3/Al2O3Composite powder pattern.
Fig. 2 is TiAl prepared by cold spraying3/Al2O3Composite coating Cross Section Morphology.
Fig. 3 is TiAl3/Al2O3Coating and basal body interface pattern after 900 DEG C of oxidation 60h of composite coating.
Specific implementation mode
In a specific embodiment, TiAl of the present invention3/Al2O3The preparation method of composite powder and its coating, is selected first
Pure Al and nano-TiO2Powder mixes certain time with certain proportion high-energy ball milling, is then heat-treated and TiAl is made3/Al2O3It is multiple
Powder is closed, then uses the method for cold air power spraying and coating at 100~700 DEG C of temperature (preferably 550~600 DEG C), pressure 0.3~
Under conditions of 5.0MPa (preferably 1.8~2.5MPa), composite powder obtained is sprayed on titanium alloy base material and is formed
TiAl3/Al2O3Composite coating.Coating composition is TiAl3And Al2O3, wherein Al2O3It is evenly distributed in the coating, coating layer thickness exists
10 μm or more.The preparation method is easy to operate, easy control of components, and obtained coating porosity is low, with matrix compatibility, binding force
It is good, there is preferable high temperature oxidation resistance, the counterdiffusion of coating and matrix can be substantially reduced, titanium conjunction can be well solved
Golden high-temperature oxydation problem.
In the present invention, cold spray apparatus refers to the Chinese invention patent (patent No.：01128130.8, Authorization Notice No.：
CN1161188C the cold air driven spray painter) mentioned.
TiAl of the present invention3/Al2O3Composite powder and coating composition are TiAl3And Al2O3, coating layer thickness at 10 μm or more,
Wherein Al2O3It is uniformly distributed in the coating.The grain size of composite powder is generally at 10~80 μm, and Al2O3In composite powder uniformly
Distribution.The thickness of composite coating is generally at 10~60 μm, and composite coating is combined with matrix in a manner of mechanical snap, and binding force is good
It is good.
To keep technical scheme of the present invention and advantage clearer, it is described in detail below in conjunction with specific embodiment.
Embodiment 1
The pure Al powder and nano-TiO for being 5~30 μm by granularity2Powder is with mass ratio 3:High-energy ball milling 2h after 1 mixing is high
Powder after energy ball milling is heat-treated 10h at 650 DEG C, prepares TiAl3/Al2O3Composite powder, with cold spray apparatus in γ-TiAl
Deposit the composite powder of preparation on matrix alloy, 500 DEG C, operating pressure 1.8MPa of operation temperature, 20 μm of coating layer thickness is compound
Two-phase is evenly distributed in coating.
As shown in Figure 1, composite powder particle size is at 30~80 μm.As shown in Fig. 2, composite coating thickness is about 20 μm,
It is well combined with matrix.As shown in figure 3, composite coating is significantly being weakened after high-temperature oxydation with the counterdiffusion of matrix.
The experimental results showed that the coating has high temperature oxidation resistance well.The performance indicator of the present embodiment is：Coating is at 900 DEG C
Weightening is less than 1.5mg/cm after lower isothermal oxidation 200h2。
Embodiment 2
The pure Al powder and nano-TiO for being 5~30 μm by granularity2Powder is with mass ratio 2:High-energy ball milling 1h after 1 mixing is high
Powder after energy ball milling is heat-treated 10h at 750 DEG C, prepares TiAl3/Al2O3Composite powder, with cold spray apparatus in γ-TiAl
The composite powder of preparation, 600 DEG C, operating pressure 2.0MPa of operation temperature, 30 μm of coating layer thickness are deposited on matrix alloy.Experiment
The result shows that the coating has high temperature oxidation resistance well.The performance indicator of the present embodiment is：Coating is inferior at 900 DEG C
Weightening is less than 2.5mg/cm after temperature oxidation 500h2。
Embodiment 3
The pure Al powder and nano-TiO for being 5~30 μm by granularity2Powder is with mass ratio 1:High-energy ball milling 2h after 1 mixing is high
Powder after energy ball milling is heat-treated 10h at 850 DEG C, prepares TiAl3/Al2O3Composite powder, with cold spray apparatus in Ti-
The composite powder of preparation, 500 DEG C, operating pressure 1.8MPa of operation temperature, coating layer thickness 10 are deposited on 22Al-26Nb matrix alloys
μm.The experimental results showed that the coating has high temperature oxidation resistance well.The performance indicator of the present embodiment is：Coating is 900
Weightening is less than 2.0mg/cm after cyclic oxidation 100 times at DEG C2。
Embodiment 4
The pure Al powder and nano-TiO for being 5~30 μm by granularity2Powder is with mass ratio 2.5:High-energy ball milling 2h after 1 mixing is high
Powder after energy ball milling is heat-treated 12h at 750 DEG C, prepares TiAl3/Al2O3Composite powder, with cold spray apparatus in γ-TiAl
The composite powder of preparation, 650 DEG C, operating pressure 2.0MPa of operation temperature, 30 μm of coating layer thickness are deposited on matrix alloy.Experiment knot
Fruit shows that the coating has high temperature oxidation resistance well.The performance indicator of the present embodiment is：Coating recycles at 900 DEG C
Oxide skin is without peeling after aoxidizing 200 times.
Claims (4)
1. a kind of TiAl3/Al2O3The application of composite powder, it is characterised in that：Composite powder ingredient is TiAl3And Al2O3, grain size
It it is 10~80 μm, and Al2O3It is uniformly distributed in composite powder；
Select pure Al and nano-TiO2Powder is with mass ratio 3:1~1:High-energy ball milling mixes 1~4h between 1, and mixed powder exists
300~800 DEG C of 2~20h of heat diffusion treatment, TiAl is generated after furnace cooling3/Al2O3Composite powder；
Select prepared TiAl3/Al2O3Composite powder, using cold air dynamic spraying technology, operating condition be temperature 100~
700 DEG C, 0.3~5.0MPa of pressure is sprayed directly on titanium alloy substrate and forms composite coating.
2. TiAl described in accordance with the claim 13/Al2O3The application of composite powder, it is characterised in that：Al2O3In composite coating
It is uniformly distributed.
3. TiAl described in accordance with the claim 13/Al2O3The application of composite powder, it is characterised in that：Composite coating is in matrix
Existing mechanical snap, binding force are good.
4. TiAl described in accordance with the claim 13/Al2O3The application of composite powder, it is characterised in that：Composite coating composition with it is multiple
Conjunction powdered ingredients are identical, and coating layer thickness is at 10 μm or more.
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| CN109207988B (en) * | 2017-07-25 | 2020-11-27 | 中国航空制造技术研究院 | Cold spraying powder for repairing surface damage of titanium alloy thin-wall part and repairing method |
| DE102017222182A1 (en) | 2017-12-07 | 2019-06-13 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | A method of depositing a titanium aluminide alloy, titanium aluminide alloy and substrate comprising a titanium aluminide alloy |
| CN111763939B (en) * | 2020-07-18 | 2022-04-01 | 新余学院 | Multi-scale TiC ceramic phase reinforced TiAl3TiAl biphase composite coating and preparation method thereof |
| CN112157269B (en) * | 2020-09-24 | 2021-11-26 | 四川大学 | Preparation method of cold spray coating based on heat treatment of aluminum alloy powder |
| CN114150313A (en) * | 2021-11-23 | 2022-03-08 | 西安文理学院 | TiAl alloy high-temperature oxidation-resistant nano thermal barrier coating and preparation method thereof |
| CN115651429B (en) * | 2022-09-03 | 2023-11-10 | 中国科学院金属研究所 | Low-temperature curing TiAl 3 -Al 2 O 3 -CuO-Cr 2 O 3 SiC composite high-emissivity coating material |
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| CN1337377A (en) * | 2001-09-20 | 2002-02-27 | 山东大学 | Intermatallic Ti-Al compound/alumina ceramic composite material and its prepn process |
| CN1323178C (en) * | 2005-09-29 | 2007-06-27 | 陕西科技大学 | Method for synthesizing Al203/TiAl composite material |
| CN100516299C (en) * | 2007-06-04 | 2009-07-22 | 西安交通大学 | Method for preparing compound coat between metals |
| CN101838809A (en) * | 2009-03-18 | 2010-09-22 | 中国科学院金属研究所 | Titanium alloy high-temperature protective coating and preparation method thereof |
| CN102134714B (en) * | 2010-01-27 | 2013-07-24 | 中国科学院金属研究所 | Alumina-reinforced high-temperature protective coating and preparation method thereof |
| CN102296289A (en) * | 2011-08-19 | 2011-12-28 | 九江学院 | Preparation method of metal ceramic coating with intermetallic compound as binding phase |
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