CN106493348A - 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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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.First from pure Al and nano-TiO2Powder is obtained TiAl to be heat-treated after certain proportion high-energy ball milling certain time3/Al2O3Composite powder, then obtained composite powder is sprayed to formation TiAl on titanium alloy base material in 100～700 DEG C of temperature under conditions of 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 more than 10 μm.Preparation method of the present invention is simple to operate, easy control of components, and obtained coating porosity is low, good with matrix compatibility, adhesion, there is preferable high temperature oxidation resistance, the counterdiffusion of coating and matrix can be substantially reduced, titanium alloy high-temperature problem of oxidation can be solved well.
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, height
Intensity, high-melting-point and excellent creep-resistant property, can be widely used for the high-temperature component of automobile or aero-engine,
It is 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.But Ti-Al alloys high temperature oxidation resistance is not enough, especially when which uses temperature more than 800
DEG C when, surface formed have protectiveness TiO2Oxide-film, at the same oxygen can penetrate in matrix with Titanium base
Solid solution is formed, low-alloyed plasticity is dropped, is had a strong impact on the performance of alloy.See document [2] A.Rahmel,
M.Schütze,and W.Quadakkers,Fundamentals of TiAl Oxidation–a Critical Review,
Mater.Corros.,1995,46(5),p 271-285.Therefore, titanium alloy under high-temperature situation using must apply
Coating is protected.
At present, the protective coating of Ti-Al alloys has many kinds.Wherein, coat of aluminide is had very with matrix alloy
Compatibility, obtains extensive research well, and traditional method for preparing coat of aluminide mainly has：Powder bag
Aluminising, hot-dipped aluminized, Electroplating Aluminum and thermal diffusion, sputtered aluminum and thermal diffusion and thermal spraying aluminum and thermal diffusion is buried,
The coat of aluminide formed using these methods is generated by the aluminium and matrix reaction that inwardly spreads.These aluminium
Although compound coating improves the antioxygenic property of matrix to a certain extent, its still Shortcomings, a side
Finishing coat fragility is higher, is also easy to produce crackle；On the other hand it is that high-temperature oxidation process floating coat is led with matrix counterdiffusion
Cause coating degradation speed fast, see 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 above-mentioned two problems in coat of aluminide is further to improve coating performance
Crucial.TiAl3/Al2O3There is inert Al in a large number in composite coating2O3, its can as coating and matrix it
Between diffusion barrier, so as to reduce coating catagen speed at high temperature；In addition composite coating is made up of particle,
Different from traditional coat of aluminide tissue, this tissue can improve the anti-crack of coating to a certain extent and expand
Exhibition ability.
Content of the invention
It is an object of the invention to provide a kind of TiAl for titanium alloy high-temperature protection3/Al2O3Composite powder and its
Preparation method and application, solve α-Ti3Al, γ-TiAl and O phases Ti2The high-temperature oxydation problem of AlNb alloys.Should
Composite powder and coating composition are TiAl3And Al2O3, with preferable resistance to high temperature oxidation and environmental embrittlement performance,
Preparation method adopts cold spraying, easy to operate, it is easy to control, and forms coating quality high.
The technical scheme is that：
A kind of TiAl3/Al2O3Composite powder, composite powder composition are TiAl3And Al2O3, particle diameter is 10～80 μm,
And Al2O3It is uniformly distributed in composite powder.
Described TiAl3/Al2O3The preparation method of composite powder, from pure Al and nano-TiO2Powder is with quality
Than 3:1～1:Between 1, high-energy ball milling mixes 1～4h, mixed powder 300～800 DEG C of heat diffusion treatments 2～
20h, generates TiAl after along with the furnace cooling3/Al2O3Composite powder.
Described TiAl3/Al2O3The application of composite powder, from prepared TiAl3/Al2O3Composite powder, adopts
With cold air dynamic spraying technology, operating condition is 100～700 DEG C of temperature, 0.3～5.0MPa of pressure, directly spray
It is coated onto formation composite coating on titanium alloy substrate.
Described TiAl3/Al2O3The application of composite powder, Al2O3It is uniformly distributed in composite coating.
Described TiAl3/Al2O3The application of composite powder, composite coating assume mechanical snap, adhesion with matrix
Well.
Described TiAl3/Al2O3The application of composite powder, composite coating composition are identical with composite powder composition, apply
Thickness degree is more than 10 μm.
The present invention design philosophy be：
Cold spraying is an emerging coat preparing technology developed in recent years, different from traditional thermal spraying,
It is the coating that formed by plastic deformation during high velocity powder particles hit matrix under low-temperature condition, because
This cold spraying is particularly suitable for the preparation of powder and basal body coating layer to heat and oxidation-sensitive.Present invention high-energy ball milling
Al/TiO2Mixed-powder and heat treatment prepare TiAl3/Al2O3Composite powder, then directly prepared by cold spraying
TiAl3/Al2O3Composite powder, forms TiAl3/Al2O3Composite coating.The method is easy to operate, it is easy to control,
High-temperature oxydation experiment shows that there is the coating antioxygenic property well, the technology not at home and abroad to be reported.
Advantages of the present invention and beneficial effect are：
1. the composite powder and coating that prepared by the present invention, include high-temperature oxydation and environment to the high temperature protection of titanium alloy
Brittle largely effective.
2. composite powder of the present invention is obtained using high-energy ball milling mixed-powder and its heat treatment method, and prepared answers
Close powder two-phase to be evenly distributed, easy control of components.
3. composite coating is prepared using cold spray-coating method.Non-oxidation in spraying process, without phase transformation, coating composition with
Composite powder is consistent, and operating process is simple.
4. the present invention is not affected on matrix alloy using cold spray-coating method prepares coating.
Description of the drawings
Fig. 1 is the TiAl for preparing3/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 embodiment
In a specific embodiment, TiAl of the present invention3/Al2O3Composite powder and its preparation method of coating, first
From pure Al and nano-TiO2Powder mixes certain time with certain proportion high-energy ball milling, is then heat-treated and is obtained
TiAl3/Al2O3Composite powder, then with the method for cold air power spraying and coating in 100～700 DEG C of temperature (preferably
550～600 DEG C), under conditions of 0.3～5.0MPa of pressure (preferably 1.8～2.5MPa), will be obtained multiple
Closing powder spray, TiAl is formed on titanium alloy base material3/Al2O3Composite coating.Coating composition is TiAl3And Al2O3,
Wherein Al2O3It is evenly distributed in the coating, coating layer thickness is more than 10 μm.The preparation method is simple to operate,
Easy control of components, obtained coating porosity are low, good with matrix compatibility, adhesion, with preferably anti-height
Warm oxidation susceptibility, can substantially reduce the counterdiffusion of coating and matrix, can solve titanium alloy high-temperature oxygen well
Change problem.
In the present invention, cold spray apparatus refer to the Chinese invention patent (patent No.：01128130.8, authorize public
Announcement number：CN1161188C the cold air driven spray painter that) mentions.
TiAl of the present invention3/Al2O3Composite powder and coating composition are TiAl3And Al2O3, coating layer thickness is at 10 μm
More than, wherein Al2O3It is uniformly distributed in the coating.The particle diameter of composite powder is typically at 10～80 μm, and Al2O3
It is uniformly distributed in composite powder.The thickness of composite coating typically at 10～60 μm, composite coating and matrix with
The mode of mechanical snap is combined, and adhesion is good.
For making technical scheme and advantage clearer, retouched below in conjunction with specific embodiment in detail
State.
Embodiment 1
By pure Al powder that granularity is 5～30 μm and nano-TiO2Powder is with mass ratio 3:High-energy ball milling after 1 mixing
2h, the powder after high-energy ball milling are heat-treated 10h at 650 DEG C, prepare TiAl3/Al2O3Composite powder, with cold
Spraying equipment deposits the composite powder of preparation, 500 DEG C of operation temperature, operating pressure on γ-TiAl matrix alloys
1.8MPa, 20 μm of coating layer thickness, in composite coating, two-phase is evenly distributed.
As shown in figure 1, composite powder particle size is at 30～80 μm.As shown in Fig. 2 composite coating thickness
About 20 μm, it is well combined with matrix.As shown in figure 3, composite coating after high-temperature oxydation with matrix
Counterdiffusion significantly weakened.Test result indicate that, the coating has high temperature oxidation resistance well.This
The performance indications of embodiment are：Coating is increased weight less than 1.5mg/cm after isothermal oxidation 200h at 900 DEG C2.
Embodiment 2
By pure Al powder that granularity is 5～30 μm and nano-TiO2Powder is with mass ratio 2:High-energy ball milling after 1 mixing
1h, the powder after high-energy ball milling are heat-treated 10h at 750 DEG C, prepare TiAl3/Al2O3Composite powder, with cold
Spraying equipment deposits the composite powder of preparation, 600 DEG C of operation temperature, operating pressure on γ-TiAl matrix alloys
2.0MPa, 30 μm of coating layer thickness.Test result indicate that, the coating has high temperature oxidation resistance well.
The performance indications of the present embodiment are：Coating is increased weight less than 2.5mg/cm after isothermal oxidation 500h at 900 DEG C2.
Embodiment 3
By pure Al powder that granularity is 5～30 μm and nano-TiO2Powder is with mass ratio 1:High-energy ball milling after 1 mixing
2h, the powder after high-energy ball milling are heat-treated 10h at 850 DEG C, prepare TiAl3/Al2O3Composite powder, with cold
Spraying equipment deposits the composite powder of preparation, 500 DEG C of operation temperature, behaviour on Ti-22Al-26Nb matrix alloys
Make pressure 1.8MPa, 10 μm of coating layer thickness.Test result indicate that, the coating has resistance to high temperature oxidation well
Performance.The performance indications of the present embodiment are：Coating cyclic oxidation at 900 DEG C increases weight afterwards for 100 times and is less than
2.0mg/cm2.
Embodiment 4
By pure Al powder that granularity is 5～30 μm and nano-TiO2Powder is with mass ratio 2.5:High energy ball after 1 mixing
Mill 2h, the powder after high-energy ball milling are heat-treated 12h at 750 DEG C, prepare TiAl3/Al2O3Composite powder, uses
Cold spray apparatus deposit the composite powder of preparation, 650 DEG C of operation temperature, operation pressure on γ-TiAl matrix alloys
Power 2.0MPa, 30 μm of coating layer thickness.Test result indicate that, the coating has high temperature oxidation resistance well.
The performance indications of the present embodiment are：Coating at 900 DEG C 200 rear oxidation skins of cyclic oxidation without peeling.
Claims (6)
1. a kind of TiAl3/Al2O3Composite powder, it is characterised in that：Composite powder composition is TiAl3And Al2O3,
Particle diameter is 10～80 μm, and Al2O3It is uniformly distributed in composite powder.
2. the TiAl described in a kind of claim 13/Al2O3The preparation method of composite powder, it is characterised in that：Choosing
With pure Al and nano-TiO2Powder is with mass ratio 3:1～1:Between 1, high-energy ball milling mixes 1～4h, mixed
Powder generates TiAl in 300～800 DEG C of 2～20h of heat diffusion treatment, after along with the furnace cooling3/Al2O3Composite powder.
3. the TiAl described in a kind of claim 1 or 23/Al2O3The application of composite powder, it is characterised in that：Choosing
With 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 into formation composite coating on titanium alloy substrate.
4. according to the TiAl described in claim 33/Al2O3The application of composite powder, it is characterised in that：Al2O3
It is uniformly distributed in composite coating.
5. according to the TiAl described in claim 33/Al2O3The application of composite powder, it is characterised in that：Compound painting
Layer assumes mechanical snap with matrix, and adhesion is good.
6. according to the TiAl described in claim 33/Al2O3The application of composite powder, it is characterised in that：Compound painting
Composition of layer is identical with composite powder composition, and coating layer thickness is more than 10 μm.
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Cited By (6)
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| CN109207988A (en) * | 2017-07-25 | 2019-01-15 | 中国航空制造技术研究院 | A kind of reparation of thin-wall workpiece surface damage cold spraying powder and restorative procedure |
| CN111763939A (en) * | 2020-07-18 | 2020-10-13 | 新余学院 | Multi-scale TiC ceramic phase reinforced TiAl3TiAl biphase composite coating and preparation method thereof |
| CN112157269A (en) * | 2020-09-24 | 2021-01-01 | 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 |
| CN115651429A (en) * | 2022-09-03 | 2023-01-31 | 中国科学院金属研究所 | Low-temperature cured TiAl 3 -Al 2 O 3 -CuO-Cr 2 O 3 -SiC composite high-radiation coating material |
| US11692273B2 (en) | 2017-12-07 | 2023-07-04 | Lufthansa Technik Ag | Method for applying a titanium aluminide alloy, titanium aluminide alloy and substrate comprising a titanium aluminide alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109207988A (en) * | 2017-07-25 | 2019-01-15 | 中国航空制造技术研究院 | A kind of reparation of thin-wall workpiece surface damage cold spraying powder and restorative procedure |
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| 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 |
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| CN115651429A (en) * | 2022-09-03 | 2023-01-31 | 中国科学院金属研究所 | Low-temperature cured TiAl 3 -Al 2 O 3 -CuO-Cr 2 O 3 -SiC composite high-radiation coating material |
| 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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