CN108637468A - A kind of preparation method of thermal barrier coating surface super hydrophobic structure - Google Patents
A kind of preparation method of thermal barrier coating surface super hydrophobic structure Download PDFInfo
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- CN108637468A CN108637468A CN201810354643.4A CN201810354643A CN108637468A CN 108637468 A CN108637468 A CN 108637468A CN 201810354643 A CN201810354643 A CN 201810354643A CN 108637468 A CN108637468 A CN 108637468A
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- barrier coating
- thermal barrier
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- water
- hydrophobic structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/60—Preliminary treatment
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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Abstract
The invention discloses a kind of preparation methods of thermal barrier coating surface super hydrophobic structure, belong to surface working process technical field.It is irradiated by the water-bath in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid of the thermal barrier coating after pre-treatment, then using femtosecond laser.The surface water drops static contact angle that the method for the present invention obtains is 139~141 °, and compared with 80.5 ° of green surface static contact angle, surface characteristic is changed into super-hydrophobicity by hydrophily, can effectively improve the anticorrosive property and automatic cleaning action of thermal barrier coating.
Description
Technical field
The invention discloses a kind of preparation methods of thermal barrier coating surface super hydrophobic structure, belong to surface working process technology
Field.
Background technology
It is well known that preparing micro-nano structure in metal material surface, it will generally pass through surface modification, could generate hydrophobic
Property, and decorative material can only generally exist at normal temperatures, this just significantly limits micro-structure hydrophobic property in extreme circumstances
Application range.Tsinghua University woods is clear can also to make its generation by constructing metal material surface micro-structure without any modification
Certain hydrophobic structure, contact angle are 121 °~134 °, show excellent hydrophobicity.Lu Zhou uses anodic oxidation-table
Method is modified in face, and aluminium oxide super hydrophobic surface is prepared on alumina-base material surface, the experimental results showed that, the potential resistance to electrolyte contamination environment of material
Corrosive power significantly improves.Although these methods for preparing surface micro-structure are relatively easy, also need to be surface modified,
And this method is not suitable for for having for the part of cooling stomata.
Currently, since the CMAS dust in air is more, in the long service of aero-engine, they can be empty by compression
Gas is brought into engine high-temperature area from atmospheric environment, these complicated CMAS dust granules diameters are generally in 2mm hereinafter, can be with
Solid particle or semi-molten liquid particles (by high temperature action) form directly impinge blade coatings surface.
CMAS dust constituents are more complicated, but mainly by CaO-MgO-Al2O3-SiO2Equal materials composition, since these are multiple
The fusing point of miscellaneous mixed oxide is relatively low, and (about 1000~1200 DEG C) can be adhered to liquid or semi liquid state at high temperature for they
In coating surface, it is then deposited on surface ceramii layer.Part CMAS again with liquid or ionic state along ceramic layer hole, defect or
Inside gap infiltration to ceramic layer between person's column crystal, to generate damage to ceramic coating performance.And it is shut down in engine
When, as temperature is reduced to room temperature, they can form layer of brittle incrustation matter in surface ceramii layer, to be applied to thermal boundary
Layer causes major injury, greatly reduces the service life of thermal barrier coating.
The damage that CMAS generates coating performance because being attached to surface ceramii layer in order to prevent, we copy lotus leaf surface to dredge
Aqueous principle designs and manufactures the bionical micro-structure of lyophoby state CMAS in coating surface, to prevent liquid or semi liquid state shape
CMAS generates adherency in surface ceramii layer and ion immerses.For this purpose, we utilize ultra-short pulsed femtosecond laser in ceramic layer table
It prepares with hydrophobic micro-nano structure in face, it is therefore an objective to hope this micro-structure that can generate part to the CMAS formed in high temperature
Alienation effect.
Femtosecond laser has very high instantaneous power, and when femtosecond laser is radiated at material surface, energy can be by material
Expect direct gasification；Femtosecond laser has very small focused radius, and in process, the damage that material is subject to is small, can be significantly
Improve the machining accuracy and surface smoothness of material；The femtosecond laser duration is very short, and the fuel factor of material is very small, can be with
It realizes " cold working " truly, realizes micro Process at the micron and nanoscale scales.
Invention content
The present invention is directed to the hydrophobic technical need of thermal barrier coating, provides a kind of preparation of thermal barrier coating hydrophobic surface
Method, the thermal barrier coating (ZrO prepared using Gold Films Irradiated by Femtosecond Laser EB-PVD2+8Y2O3) surface, it prepares with certain super-hydrophobic
The surface micro-structure of performance, preparation process is simple, easy to operate.
A kind of preparation method on super-hydrophobicity thermal barrier coating surface, the specific steps are：
1, pre-treatment：By thermal barrier coating (ZrO2+8Y2O3) first cleaned with deionized water, then use first successively in sequence
Benzene, acetone, chloroform, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 20 minutes respectively.
2, it pre-processes：First by thermal barrier coating water-bath in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid, then spend again from
Sub- water cleaning, is finally cleaned by ultrasonic 20 minutes, last nitrogen is blown respectively in deionized water, acetone, ethyl alcohol successively in sequence
It is dry.Hydrogen peroxide concentration is 30%, the concentrated sulfuric acid a concentration of 96%~98%, volume ratio 3：7, bath temperature is 85 DEG C, when water-bath
Between be 50-70 minutes.
3, Gold Films Irradiated by Femtosecond Laser：Control single pulse energy, the parameters such as sweep speed, the thermal barrier coating obtained to step (2)
It is irradiated.Irradiation time is longer, and working (finishing) area is bigger.
4, femtosecond laser wavelength 800nm, pulsewidth 240fs, repetition 1KHz, single pulse energy are 0.3~2W, and sweep speed is
50mm/s, processing spot center is away from D=35~50 μm；It is preferred that 45 μm.
Beneficial effects of the present invention：
The surface water drops static contact angle that the method for the present invention obtains is 139~141 °, with green surface static contact angle
80.5 ° are compared, and surface characteristic is changed into super-hydrophobicity by hydrophily, can effectively improve the anticorrosive property of thermal barrier coating and from clearly
Clean effect.
Description of the drawings
Fig. 1 is undressed thermal barrier coating (ZrO2+8Y2O3) surface SEM and surface contact angle；
Fig. 2 is thermal barrier coating (ZrO prepared by embodiment 12+8Y2O3) gained surface SEM and surface contact angle；
Fig. 3 is thermal barrier coating (ZrO prepared by embodiment 22+8Y2O3) gained surface SEM and surface contact angle；
Fig. 4 is thermal barrier coating (ZrO prepared by embodiment 32+8Y2O3) gained surface SEM and surface contact angle.
Specific implementation mode
After now the embodiment of the present invention is described in, but the present invention should not be limited only to embodiment.
Embodiment 1：A kind of preparation method of thermal barrier coating surface super hydrophobic structure, the specific steps are：
1, pre-treatment：Thermal barrier coating is first cleaned with deionized water, then in sequence successively use toluene, acetone, chloroform,
Absolute ethyl alcohol, deionized water are cleaned by ultrasonic 20 minutes respectively.
2, it pre-processes：First by thermal barrier coating water-bath in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid, then again by thermal boundary
Coating (ZrO2+8Y2O3) sample cleans with deionized water, finally in sequence successively in deionized water, acetone, ethyl alcohol respectively
It is cleaned by ultrasonic 20 minutes, last nitrogen drying.Hydrogen peroxide concentration is 30%, the concentrated sulfuric acid a concentration of 96%~98%, bath temperature
It it is 85 DEG C, water bath time is 50-70 minutes.
3, Gold Films Irradiated by Femtosecond Laser：Control single pulse energy, the parameters such as sweep speed, the thermal barrier coating obtained to step (2)
(ZrO2+8Y2O3) specimen surface irradiated.
4, femtosecond laser wavelength 800nm, pulsewidth 240fs, repetition 1KHz, processing spot center is away from 50 μm, 22 μ of spot size
M, single pulse energy 0.3W, sweep speed 50mm/s.
The contact angle of green surface is as shown in Figure 1, contact angle is 80.5 °.Thermal barrier coating (ZrO manufactured in the present embodiment2
+8Y2O3) surface SEM and contact angle it is as shown in Figure 2.As can be seen from Figure 2, gained surface static contact angle is 139.2 °, compared to not
There is 80.5 ° or so of finished surface static contact angle, surface characteristic is changed into super-hydrophobicity by hydrophily.
Embodiment 2：A kind of preparation method of thermal barrier coating surface super hydrophobic structure, the specific steps are：
1, pre-treatment：Thermal barrier coating is first cleaned with deionized water, then in sequence successively use toluene, acetone, chloroform,
Absolute ethyl alcohol, deionized water are cleaned by ultrasonic 20 minutes respectively.
2, it pre-processes：First by thermal barrier coating water-bath in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid, then again by thermal boundary
Coating (ZrO2+8Y2O3) sample cleans with deionized water, finally in sequence successively in deionized water, acetone, ethyl alcohol respectively
It is cleaned by ultrasonic 20 minutes, is finally dried up with nitrogen.Hydrogen peroxide concentration is 30%, the concentrated sulfuric acid a concentration of 96%~98%, water-bath temperature
Degree is 85 DEG C, and water bath time is 50-70 minutes.
3, Gold Films Irradiated by Femtosecond Laser：Control single pulse energy, the parameters such as sweep speed, the thermal barrier coating obtained to step (2)
(ZrO2+8Y2O3) specimen surface irradiated.
4, femtosecond laser wavelength 800nm, pulsewidth 240fs, repetition 1KHz, processing spot center is away from D=45 μm, spot size
22 μm, single pulse energy 0.3W, sweep speed 50mm/s.
Thermal barrier coating (ZrO manufactured in the present embodiment2+8Y2O3) surface SEM and contact angle it is as shown in Figure 3.It can from Fig. 3
Know, gained surface static contact angle be 141.5 °, compare 80.5 ° or so of no finished surface static contact angle, surface characteristic by
Hydrophily is changed into super-hydrophobicity.
Embodiment 3：A kind of preparation method of thermal barrier coating surface super hydrophobic structure, the specific steps are：
1, pre-treatment：Thermal barrier coating is first cleaned with deionized water, then in sequence successively use toluene, acetone, chloroform,
Absolute ethyl alcohol, deionized water are cleaned by ultrasonic 20 minutes respectively.
2, it pre-processes：First by thermal barrier coating water-bath in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid, then again by thermal boundary
Coating (ZrO2+8Y2O3) sample cleans with deionized water, finally in sequence successively in deionized water, acetone, ethyl alcohol respectively
It is cleaned by ultrasonic 20 minutes, is finally dried up with nitrogen.Hydrogen peroxide concentration is 30%, the concentrated sulfuric acid a concentration of 96%~98%, water-bath temperature
Degree is 85 DEG C, and water bath time is 50-70 minutes.
3, Gold Films Irradiated by Femtosecond Laser：Control single pulse energy, the parameters such as sweep speed, the thermal barrier coating obtained to step (2)
(ZrO2+8Y2O3) specimen surface irradiated.
4, femtosecond laser wavelength 800nm, pulsewidth 240fs, repetition 1KHz, processing spot center is away from 35 μm, 22 μ of spot size
M, single pulse energy 0.3W, sweep speed 50mm/s.
Thermal barrier coating (ZrO manufactured in the present embodiment2+8Y2O3) surface SEM and contact angle it is as shown in Figure 4.It can from Fig. 4
Know, gained surface static contact angle be 139.8 °, compare 80.5 ° or so of no finished surface static contact angle, surface characteristic by
Hydrophily is changed into super-hydrophobicity.
Claims (5)
1. a kind of preparation method of thermal barrier coating surface super hydrophobic structure, which is characterized in that be as follows：After pre-treatment
Thermal barrier coating ZrO2+8Y2O3Gold Films Irradiated by Femtosecond Laser, heat are used after water-bath, cleaning in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid
Barrier coating ZrO2+8Y2O3Surface characteristic is changed into super-hydrophobicity by hydrophily, improves the anticorrosive property and automatically cleaning of thermal barrier coating
Effect.
2. a kind of preparation method of thermal barrier coating surface super hydrophobic structure as described in claim 1, which is characterized in that described
Pre-treatment refers to：By thermal barrier coating ZrO2+8Y2O3It is first cleaned with deionized water, then uses toluene, acetone, chlorine successively in sequence
Imitative, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 20 minutes respectively.
3. a kind of preparation method of thermal barrier coating surface super hydrophobic structure as described in claim 1, which is characterized in that hydrogen peroxide
A concentration of 30%, the concentrated sulfuric acid a concentration of 96%~98%, the volume ratio of hydrogen peroxide and the concentrated sulfuric acid is 3 in mixed solution：7, water-bath
Temperature is 85 DEG C, and water bath time is 50-70 minutes；The cleaning refers to：Cleaned with deionized water, according still further to sequentially successively go from
It is cleaned by ultrasonic respectively in sub- water, acetone, ethyl alcohol 20 minutes, last nitrogen drying.
4. a kind of preparation method of thermal barrier coating surface super hydrophobic structure as described in claim 1, which is characterized in that described to fly
The technological parameter of second laser is：Femtosecond laser wavelength 800nm, pulsewidth 240fs, repetition 1KHz, single pulse energy are 0.3~2W,
Sweep speed is 50mm/s, and processing spot center is away from D=35~50 μm；Irradiation time is longer, and working (finishing) area is bigger.
5. a kind of preparation method of thermal barrier coating surface super hydrophobic structure as claimed in claim 4, which is characterized in that processing light
D=45 μm of spot centre-to-centre spacing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041470A (en) * | 2019-11-18 | 2020-04-21 | 江苏大学 | Method for preparing thermal barrier coating detached CMAS surface by picosecond laser |
| CN111099893A (en) * | 2019-12-04 | 2020-05-05 | 天津大学 | Method for improving melting resistance CMAS corrosion of thermal barrier coating by laser surface treatment |
| CN113652687A (en) * | 2021-08-16 | 2021-11-16 | 西南交通大学 | Thermal barrier coating textured anti-sticking surface and preparation method thereof |
| CN114032506A (en) * | 2021-11-09 | 2022-02-11 | 北京航空航天大学 | Thermal barrier coating with melting CMAS erosion resistance and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219770A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser modeling method for semiconductor material micro-nano multi-scale function surface |
| CN101219506A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser production method for metal base ultra-hydrophobicity micro-structure surface |
| CN101531335A (en) * | 2009-04-08 | 2009-09-16 | 西安交通大学 | Method for preparing metal surface superhydrophobic microstructure by femto-second laser |
| CN104498957A (en) * | 2014-12-17 | 2015-04-08 | 中国航空工业集团公司北京航空制造工程研究所 | Preparation method of super-hydrophobic micro-nano structure on titanium alloy surface |
| CN104625415A (en) * | 2014-12-17 | 2015-05-20 | 中国航空工业集团公司北京航空制造工程研究所 | Method and device for preparing bionic super-hydrophobic micro-nano surface through femtosecond laser |
| CN105479009A (en) * | 2016-02-02 | 2016-04-13 | 深圳光韵达光电科技股份有限公司 | Preparation method of super-hydrophobic structure on surface of SMT template |
| CN105555467A (en) * | 2013-09-04 | 2016-05-04 | 西门子能源公司 | Method for forming three-dimensional anchoring structures on a surface by propagating energy through a multi-core fiber |
| CN106583930A (en) * | 2016-12-07 | 2017-04-26 | 合肥工业大学 | Method for achieving reversible wettability of titanium sheet based on femtosecond laser direct writing |
-
2018
- 2018-04-19 CN CN201810354643.4A patent/CN108637468A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219770A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser modeling method for semiconductor material micro-nano multi-scale function surface |
| CN101219506A (en) * | 2008-01-07 | 2008-07-16 | 江苏大学 | Laser production method for metal base ultra-hydrophobicity micro-structure surface |
| CN101531335A (en) * | 2009-04-08 | 2009-09-16 | 西安交通大学 | Method for preparing metal surface superhydrophobic microstructure by femto-second laser |
| CN105555467A (en) * | 2013-09-04 | 2016-05-04 | 西门子能源公司 | Method for forming three-dimensional anchoring structures on a surface by propagating energy through a multi-core fiber |
| CN104498957A (en) * | 2014-12-17 | 2015-04-08 | 中国航空工业集团公司北京航空制造工程研究所 | Preparation method of super-hydrophobic micro-nano structure on titanium alloy surface |
| CN104625415A (en) * | 2014-12-17 | 2015-05-20 | 中国航空工业集团公司北京航空制造工程研究所 | Method and device for preparing bionic super-hydrophobic micro-nano surface through femtosecond laser |
| CN105479009A (en) * | 2016-02-02 | 2016-04-13 | 深圳光韵达光电科技股份有限公司 | Preparation method of super-hydrophobic structure on surface of SMT template |
| CN106583930A (en) * | 2016-12-07 | 2017-04-26 | 合肥工业大学 | Method for achieving reversible wettability of titanium sheet based on femtosecond laser direct writing |
Non-Patent Citations (2)
| Title |
|---|
| 刘纯波等: "热障涂层的研究现状与发展趋势 ", 《中国有色金属学报》 * |
| 刘纯波等: "热障涂层的研究现状与发展趋势", 《中国有色金属学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041470A (en) * | 2019-11-18 | 2020-04-21 | 江苏大学 | Method for preparing thermal barrier coating detached CMAS surface by picosecond laser |
| CN111099893A (en) * | 2019-12-04 | 2020-05-05 | 天津大学 | Method for improving melting resistance CMAS corrosion of thermal barrier coating by laser surface treatment |
| CN111099893B (en) * | 2019-12-04 | 2022-03-22 | 天津大学 | Method for improving melting resistance CMAS corrosion of thermal barrier coating by laser surface treatment |
| CN113652687A (en) * | 2021-08-16 | 2021-11-16 | 西南交通大学 | Thermal barrier coating textured anti-sticking surface and preparation method thereof |
| CN114032506A (en) * | 2021-11-09 | 2022-02-11 | 北京航空航天大学 | Thermal barrier coating with melting CMAS erosion resistance and preparation method thereof |
| CN114032506B (en) * | 2021-11-09 | 2023-10-03 | 北京航空航天大学 | Thermal barrier coating with anti-melting CMAS erosion function and preparation method thereof |
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