CN1274879C - Oceanic atmosphere corrosion resistant thermal barrier coating - Google Patents

Oceanic atmosphere corrosion resistant thermal barrier coating Download PDF

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CN1274879C
CN1274879C CN 200410101398 CN200410101398A CN1274879C CN 1274879 C CN1274879 C CN 1274879C CN 200410101398 CN200410101398 CN 200410101398 CN 200410101398 A CN200410101398 A CN 200410101398A CN 1274879 C CN1274879 C CN 1274879C
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barrier coating
thermal barrier
layer
ceramic layer
corrosion resistant
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CN1635178A (en
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宫声凯
刘晓
徐惠彬
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Beihang University
Beijing University of Aeronautics and Astronautics
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties

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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The present invention discloses a thermal barrier coating for resisting oceanic atmosphere corrosion. The present invention adopts a cathode beam physical vapor deposition method to prepare an alpha-alumina (alpha-Al2O3) thin coating on the surface layer of a ceramic coating so as to prevent the yttrium oxide (Y2O3) in zirconia (ZrO2) with stable yttrium oxide (Y2O3), which is used as the ceramic coating, from eroding by corrosive atmospheres; therefore, the corrosion resistance of the thermal barrier coating is enhanced.

Description

A kind of oceanic atmosphere corrosion resistant thermal barrier coating
Technical field
The present invention relates to a kind of heat barrier coat material, specifically, be meant that a kind of electro beam physics vapour deposition method that adopts prepares certain thickness αYang Hualv (α-Al on the top layer of ceramic layer 2O 3) improve the novel thermal barrier coating of the erosion resistance of thermal barrier coating.
Background technology
Along with the development of modern high technology, particularly under the hot environment of gas turbine engine, the independent use of existing metallic substance can not be satisfied design and operational requirement.Thermal barrier coating is a kind of surface heat guard technology that develops nineteen sixties, its design philosophy is performances such as high temperature resistant, anticorrosive and low heat conduction of utilizing stupalith superior, mode with coating is mutually compound with metallic matrix with pottery, when improving metal fever end pieces resistance to high temperature corrosion ability, make it can bear higher use temperature, and have the working temperature that improves engine, prolong the hot-end component effect in work-ing life.
The thermal barrier coating structure that adopts is essentially the bilayer structure that is made of ceramic layer and tack coat at present.Its preparation method mainly contains electro beam physics vapour deposition and plasma spraying.Ceramic layer material is mainly yttrium oxide (Y 2O 3) stable zirconium white (ZrO 2), i.e. YSZ.Yet,, cause the yttrium oxide (Y among the YSZ owing to have vanadium (V), sulphur aggressive atmospheres such as (S) inevitably in the combustion gas of gas turbine engine 2O 3) be etched and lose mutually stable effect, cause zirconium white (ZrO 2) phase transformation from square phase (t ' phase) to monocline phase (m phase) takes place will be to room temperature from high temperature the time, volumetric expansion is about about 4%, generation stress spalling failure.Therefore, design novel thermal barrier coating structure, control the yttrium oxide (Y among the YSZ effectively 2O 3) not being corroded property atmosphere erosion, the corrosion resistance of raising thermal barrier coating is vital to the service life that improves thermal barrier coating.
αYang Hualv (α-Al 2O 3) at high temperature have favorable tissue and structural stability, and αYang Hualv (α-Al 2O 3) vitriol and vanadium erosion are had stronger corrosion resistance, therefore, can on ceramic layer, prepare one deck αYang Hualv (α-Al 2O 3) change gas turbine engine and be subjected to vanadium (V), sulphur aggressive atmosphere corrosive abilities such as (S) at work.
Summary of the invention
The objective of the invention is to disclose a kind of heat barrier coat material of oceanic atmosphere corrosion resistant, is to adopt the electro beam physics vapour deposition method to prepare on the ceramic layer surface to have certain thickness αYang Hualv (α-Al 2O 3) control yttrium oxide (Y effectively as ceramic layer 2O 3) stable zirconium white (ZrO 2) in yttrium oxide (Y 2O 3) not being corroded property atmosphere corrode, thereby increase substantially the corrosion resistance of thermal barrier coating, improve the service life of thermal barrier coating.
The present invention is a kind of oceanic atmosphere corrosion resistant thermal barrier coating, comprises ceramic layer, tack coat, etch resistant layer, and ceramic layer material is yttrium oxide Y 2O 3Stable zirconium white ZrO 2Bonding layer material is that (Ni, Co, Cr, Al, Y) alloy material, its weight percent are 18～22% cobalt, 19～25% chromium, 6～8% aluminium, 0.07～1.0% yttrium and the nickel of surplus to Ni, Co, Cr aluminium yttrium; The etch resistant layer material is αYang Hualv (α-Al 2O 3); Being tack coat on the outside surface of described coated substrate, is ceramic layer on the outside surface of tack coat, is etch resistant layer on the outside surface of ceramic layer.
The preparation method of described oceanic atmosphere corrosion resistant thermal barrier coating is with etch resistant layer αYang Hualv (α-Al 2O 3) adopt the electro beam physics vapour deposition method to be deposited on the surface of ceramic layer (YSZ).
The preparation method of described oceanic atmosphere corrosion resistant thermal barrier coating, its etch resistant layer αYang Hualv (α-Al 2O 3) deposit thickness is 5～10 μ m.
Described oceanic atmosphere corrosion resistant thermal barrier coating adopts continuously and for the salt coacervation anticorrosive thermal barrier coating sample is carried out 950 ℃ of insulation 30min, and air cooling 10min carries out the sodium sulfate salt (Na of reciprocation cycle to room temperature 2SO 4)+oxidation alum (5wt.%V 2O 5) the thermal etching experimental result shows that the anticorrosive life-span has been improved 2～4 times than common double-deck thermal barrier coating.
The advantage of oceanic atmosphere corrosion resistant thermal barrier coating of the present invention: (1) etch resistant layer adopts αYang Hualv (α-Al 2O 3) material is as the skin of thermal barrier coating, so improved the resistance to high temperature oxidation and the corrosive nature of thermal barrier coating; (2) adopt the method for sophisticated electro beam physics vapour deposition to prepare coating, its preparation technology is easy, and technology is controlled; (3) thermal barrier coating of structure of the present invention is compared its corrosion resistance at 950 ℃ of insulation 30min with the bilayer structure thermal barrier coating, and air cooling 10min is to the sodium sulfate salt (Na of room temperature reciprocation cycle 2SO 4)+oxidation alum (5wt.%V 2O 5) anticorrosive life-span in the environment improved 2～4 times.
Description of drawings
Fig. 1 is a thermal barrier coating structural representation of the present invention.
Fig. 2 is an electro beam physics vapour deposition equipment synoptic diagram.
Fig. 3 (a) is common double-deck thermal barrier coating surface topography XRD figure sheet.
Fig. 3 (b) is a thermal barrier coating upper layer pattern XRD figure sheet of the present invention.
Fig. 4 is thermal circulation performance detection curve figure.
Fig. 5 carries out hot corrosion resistance detection curve figure in sodium sulfate salt solution.
Fig. 6 carries out hot corrosion resistance detection curve figure in sodium sulfate salt and oxidation alum (5wt.%) solution.
Among the figure: 1. the vacuum chamber 2a. first crucible 2b. second crucible 2c. the 3rd crucible
3. etch resistant layer charge bar 4. tack coat charge bars 5. ceramic layer charge bars 6. baffle plates 7. rotary plate framves
8. electron beam gun 9. electron beam gun 10. substrates 11. tack coats 12. ceramic layers
13. etch resistant layer 14. matrixes
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is the anticorrosive thermal barrier coating of a kind of oceanic atmosphere, is made of ceramic layer, tack coat and etch resistant layer, and ceramic layer material is that YSZ is yttrium oxide (Y 2O 3) stable zirconium white (ZrO 2), bonding layer material is that (Ni, Co, Cr, Al, Y) alloy material, its weight percent are 18～22% cobalt, 19～25% chromium, 6～8% aluminium, 0.07～1.0% yttrium and the nickel of surplus to Ni, Co, Cr aluminium yttrium, and the etch resistant layer material is αYang Hualv (α-Al 2O 3); Being tack coat on the outside surface of described coated substrate, is ceramic layer on the outside surface of tack coat, is etch resistant layer on the outside surface of ceramic layer.
Design philosophy of the present invention is: utilize αYang Hualv (α-Al 2O 3) at high temperature have favorable tissue and structural stability and to vitriol and the stronger corrosion resistance of vanadium erosion, at yttrium oxide (Y 2O 3) stable zirconium white (ZrO 2) top layer of ceramic layer adopts the method preparation of electro beam physics vapour deposition to have certain thickness αYang Hualv (α-Al 2O 3), thereby the corrosion resistance of raising thermal barrier coating.Its objective is the yttrium oxide (Y that controls effectively as ceramic layer 2O 3) stable zirconium white (ZrO 2) in yttrium oxide (Y 2O 3) not being corroded property atmosphere corrode, thereby increase substantially the corrosion resistance of thermal barrier coating, improve the service life of thermal barrier coating.
In the present invention, adopt the method preparation of electro beam physics vapour deposition to have anticorrosive thermal barrier coating, its technical process is:
One, preparation charge bar:
(A) preparation bonding layer material charge bar
Take by weighing in proportion Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y) alloying element, 1400 ℃～1600 ℃ of smelting temperatures make the tack coat charge bar through melting;
(B) preparation ceramic layer material charge bar
Zirconium white (ZrO with stabilized with yttrium oxide 2+ (6-8wt%) Y 2O 3) powder makes ceramic charge bar through sintering;
(C) preparation etch resistant layer material charge bar
With αYang Hualv (α-Al 2O 3) the repressed etch resistant layer charge bar that sinters into of powder.
Two, adopt electro beam physics vapour deposition equipment to prepare coating:
(A) the above-mentioned charge bar that makes is put into 3 crucibles of electro beam physics vapour deposition equipment respectively, and the nickel base superalloy matrix is installed on the substrate 10;
(B) be evacuated to required vacuum tightness～10 -4Pa;
(C) the speed of rotation 10～20rpm of setting rotary plate frame 7;
Adopt 10 to 600～900 ℃ of electron beam heated substrates, electron-beam voltage 17～19kV;
(D) deposition tack coat: prevapourising bonding layer material charge bar, and regulate electronic beam current 1.4～1.8A, charge bar climbing speed 0.8～1.0mm/min, sedimentation rate 1.5～2.0 μ m/min; Draw back baffle plate 6, the hydatogenesis tack coat begins, and takes out after deposition is finished, and puts into vacuum heat treatment furnace and carries out vacuum heat treatment 2～6hrs, 1000～1100 ℃ of thermal treatment temps;
(E) deposited ceramic layer: will be installed on the substrate 10 of electro beam physics vapour deposition equipment through the nickel base superalloy matrix 14 after (D) handles, and regulate rotary plate frame 7 to the second crucible 2b top that stupalith is housed, regulate electronic beam current 1.4～1.8A, charge bar climbing speed 1.2～1.6mm/min, sedimentation rate 2.5～3.0 μ m/min; Draw back baffle plate 6, the hydatogenesis ceramic layer begins, closed baffle plate 6 after deposition is finished;
(F) deposition etch resistant layer: will be installed on the substrate 10 of electro beam physics vapour deposition equipment through the nickel base superalloy matrix 14 after (E) handles, and regulate rotary plate frame 7 to the crucible 2c top that the αYang Hualv stupalith is housed, regulate electronic beam current 0.6～0.8A, charge bar climbing speed 0.5～0.9mm/min, sedimentation rate 0.5～1.0 μ m/min; Draw back baffle plate 6, hydatogenesis αYang Hualv ceramic layer begins, and takes out after deposition is finished, and promptly anticorrosive thermal barrier coating preparation is finished.
The thermal barrier coating that adopts the electro beam physics vapour deposition method to prepare to have tack coat, ceramic layer and etch resistant layer (structure as shown in Figure 1, surface topography is shown in Fig. 3 (b)).Concrete preparation technology is as follows:
Tack coat 11: Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y) component is 49.3% nickel by weight percentage, 20% cobalt, 22% chromium, 8% aluminium, 0.7% yttrium are made the alloy charge bar of diameter 70mm, long 200mm behind vacuum induction melting;
Ceramic layer 12: the zirconium white of stabilized with yttrium oxide is made diameter 70mm through sintering, the charge bar of long 200mm;
Etch resistant layer 13: with αYang Hualv (α-Al 2O 3) the repressed diameter 70mm that sinters into of powder, the charge bar of long 100mm.
Matrix 14 is nickel (Ni) based high-temperature alloy.
In vacuum tightness is 5 * 10 -4Pa, substrate 10 speed of rotation are 15rpm, 750 ℃ of substrate 10 temperature; Alloy charge bar climbing speed is that 0.8mm/min, electron beam current are the tack coat 11 that 1.6A evaporation thickness is about 50 μ m; With ceramic charge bar climbing speed is that 1.4mm/min, electron beam current are the ceramic layer 12 that 1.5A hydatogenesis thickness is about 150 μ m; With αYang Hualv charge bar climbing speed is that 0.6mm/min, electron beam current are the αYang Hualv layer 13 that 0.7A hydatogenesis thickness is about 10 μ m.
In the present invention, in order to test the corrosion resistance nature of etch resistant layer 13, adopt the etch resistant layer of in the preparation process of the same terms, making three kinds of different thickness 5 μ m, 10 μ m, 20 μ m to carry out the test of performances such as cyclic oxidation weightening finish, corrosion and heat resistant.
The anticorrosive thermal barrier coating of above-mentioned three kinds of different thickness is carried out the thermal etching experiment finds, for the environment that does not have vitriol and vanadium, double-deck thermal barrier coating be coated with 5 μ m α-Al 2O 3Thermal barrier coating circulation all not inefficacies in 200 hours, and be coated with 10 μ m α-Al 2O 3Thermal barrier coating promptly began at 120 hours to lose efficacy; The double-deck thermal barrier coating life-span is about 30 times in the corrosive environment is arranged, and is coated with 10 μ m α-Al 2O 3The thermal barrier coating life-span be about 60 times, and be coated with 5 μ m α-Al 2O 3The thermal barrier coating life-span be about 120 times.This explanation is by applying 5 μ m α-Al 2O 3Ceramic layer has improved the corrosion resistance of thermal barrier coating greatly under the situation that does not influence its original life-span.So on the ceramic layer of common double-deck thermal barrier coating, adopt electro beam physics vapour deposition method plating etch resistant layer α-Al 2O 3Thickness should be smaller or equal to 10 μ m.
Thermal circulation performance detects: traditional bilayer structure thermal barrier coating and corrosion and heat resistant thermal barrier coating of the present invention are carried out thermal cycling as follows: sample is heated 30min in 1100 ℃ of air, forcing blast-cold 5min to carry out reciprocation cycle to room temperature then, cycle index and changes in weight when record lost efficacy, corrosion and heat resistant layer 13 thickness that sample is selected for use are 5 μ m, 20 μ m, adopt the warm recycle unit of automatic height to test.Test result is as shown in Figure 4: the heat resistanceheat resistant cycle performance of the corrosion and heat resistant barrier coating hot in nature of the thick αYang Hualv layer of surface-coated 5 μ m is compared with traditional bilayer structure thermal barrier coating and is not changed basically.The heat resistanceheat resistant cycle performance of the corrosion and heat resistant barrier coating hot in nature of the thick αYang Hualv layer of surface-coated 20 μ m is compared with traditional bilayer structure thermal barrier coating, and oceanic atmosphere corrosion resistant thermal barrier coating of the present invention begins to take place peeling phenomenon after circulating 500 hours.
Thermal shock resistance: employing etch resistant layer 13 thickness are that the of the present invention anticorrosive thermal barrier coating sample of 5 μ m, 20 μ m carries out thermal shock test, test conditions is 1100 ℃ of heating 15 minutes, put into cold water then rapidly and cool off, times of thermal cycle when record peels off.Test result is as shown in table 1.
Table 1 thermal shock resistance test chart
Sample Uncoated αYang Hualv layer Thickness 5 μ m Thickness 20 μ m
The heat shock resistance number of times 20 30 27
The thermal shock resistance that the corrosion and heat resistant barrier coating hot in nature that applies the αYang Hualv layer is described the slightly increase of comparing with traditional bilayer structure thermal barrier coating.
Hot corrosion resistance detects (1): adopt to supply the salt coacervation continuously, above-mentioned three kinds of samples are carried out sodium sulfate salt (Na 2SO 4) the thermal etching experiment, experiment condition is 950 ℃ of insulation 30min, air cooling 10min carries out reciprocation cycle to room temperature, and cycle index and changes in weight when record lost efficacy, test-results is as shown in Figure 5.As can be seen, the αYang Hualv layer thickness is during less than 10 μ m, the sulfuric-resisting sodium salt (Na of novel anti thermal etching thermal barrier coating 2SO 4) the thermal etching cycle performance compares with traditional bilayer structure thermal barrier coating and remain unchanged basically.
Hot corrosion resistance detects (2): adopt to supply the salt coacervation continuously, above-mentioned three kinds of samples are carried out sodium sulfate salt (Na 2SO 4)+oxidation alum (5wt.%V 2O 5) the thermal etching experiment, experiment condition is 950 ℃ of insulation 30min, air cooling 10min carries out reciprocation cycle to room temperature, and cycle index and changes in weight when record lost efficacy, test-results is as shown in Figure 6.As can be seen, traditional bilayer structure thermal barrier coating has begun to lose efficacy less than 40 hours in circulation, and anticorrosive thermal barrier coating of the present invention just slightly peels off after greater than 120 hours, and the anticorrosive life-span improves more than 3 times.

Claims (4)

1. an oceanic atmosphere corrosion resistant thermal barrier coating comprises ceramic layer, tack coat, and ceramic layer material is the zirconium white of stabilized with yttrium oxide; Bonding layer material is a Ni, Co, Cr aluminium yittrium alloy material, its weight percent is 18～22% cobalt, 19～25% chromium, 6～8% aluminium, 0.07～1.0% yttrium and the nickel of surplus, it is characterized in that: also comprise etch resistant layer, the etch resistant layer material is a αYang Hualv; Being tack coat on the outside surface of described coated substrate, is ceramic layer on the outside surface of tack coat, is etch resistant layer on the outside surface of ceramic layer.
2. the preparation method of oceanic atmosphere corrosion resistant thermal barrier coating according to claim 1 is characterized in that: described etch resistant layer αYang Hualv is to adopt the electro beam physics vapour deposition method to be deposited on the surface of ceramic layer.
3. the preparation method of oceanic atmosphere corrosion resistant thermal barrier coating according to claim 2, it is characterized in that: described etch resistant layer αYang Hualv deposit thickness is 5～10 μ m.
4. oceanic atmosphere corrosion resistant thermal barrier coating according to claim 1, it is characterized in that: adopt continuously and anticorrosive thermal barrier coating sample is carried out 950 ℃ of insulation 30min for the salt coacervation, sodium sulfate salt+5wt.% oxidation alum thermal etching experimental result that air cooling 10min carries out reciprocation cycle to room temperature shows that the anticorrosive life-span has been improved 2～4 times than common double-deck thermal barrier coating.
CN 200410101398 2004-12-21 2004-12-21 Oceanic atmosphere corrosion resistant thermal barrier coating Expired - Fee Related CN1274879C (en)

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Publication number Priority date Publication date Assignee Title
CN100393909C (en) * 2006-05-11 2008-06-11 北京航空航天大学 Method for depositing thermal barrier coating of porous dentrite ceramic layer by electron beam physical vapor deposition process
CN101876061B (en) * 2009-12-04 2012-01-25 北京科技大学 Method for forming strong combination thermal barrier coating
CN102127738B (en) * 2010-11-25 2013-01-30 北京航空航天大学 Multilayer thermal barrier coating and preparation method thereof
CN106191752A (en) * 2015-03-10 2016-12-07 中国农业机械化科学研究院 A kind of thermal barrier coating melt surface deposit protective coating and preparation method thereof
CN106917093A (en) * 2015-12-24 2017-07-04 通用电气公司 Protection product enable its can anti-sulphates corrosive method and the product with improved Sulfate corrosion resistance
CN109554706A (en) * 2018-11-14 2019-04-02 南京航空航天大学 A kind of high-temperature alloy surface TBC/Al composite thermal barrier coating and preparation method thereof
CN113073285B (en) * 2021-03-23 2023-04-07 广东省科学院新材料研究所 Thermal barrier coating and preparation method and application thereof
CN113684439A (en) * 2021-08-24 2021-11-23 湖南威斯康新材料科技有限公司 Preparation method of yttrium oxide thermal barrier coating

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