CN114231886B - High-temperature long-life YSZ coating and preparation method thereof - Google Patents
High-temperature long-life YSZ coating and preparation method thereof Download PDFInfo
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- CN114231886B CN114231886B CN202111583210.4A CN202111583210A CN114231886B CN 114231886 B CN114231886 B CN 114231886B CN 202111583210 A CN202111583210 A CN 202111583210A CN 114231886 B CN114231886 B CN 114231886B
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- 238000000576 coating method Methods 0.000 title claims abstract description 107
- 239000011248 coating agent Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 82
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000007750 plasma spraying Methods 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 19
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 239000010431 corundum Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000000889 atomisation Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002609 medium Substances 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 5
- WBWONMNLLGVERE-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid hexahydrate Chemical compound O.O.O.O.O.O.OC(=O)CC(O)(C(O)=O)CC(O)=O WBWONMNLLGVERE-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
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- 238000009826 distribution Methods 0.000 claims description 4
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- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
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- 238000009832 plasma treatment Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 6
- 239000012720 thermal barrier coating Substances 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 2
- -1 zirconium ions Chemical class 0.000 abstract description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 87
- 238000005245 sintering Methods 0.000 description 24
- 239000010410 layer Substances 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 238000010791 quenching Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000027311 M phase Effects 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
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- 239000011148 porous material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000005118 spray pyrolysis Methods 0.000 description 4
- 241001675646 Panaceae Species 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010285 flame spraying Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910002083 4 mol-% Y2O3 partially Stabilized ZrO2 Inorganic materials 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
- C04B35/488—Composites
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
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- C04B35/62665—Flame, plasma or melting treatment
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- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
Abstract
The invention discloses a high-temperature long-life YSZ coating and a preparation method thereof, wherein the YSZ coating is prepared by forming a YSZ ceramic layer on a bonding layer by spraying spherical thin-wall hollow nano t' -YSZ powder through an atmospheric plasma spraying process; the spherical thin-wall empty shell nano t' -YSZ powder is prepared from fully stable tetragonal YSZ powder through centrifugal drying and granulating. The method provided by the invention has the advantages that the raw materials react uniformly on an atomic scale, zirconium ions are prevented from being hydrolyzed, so that zirconium oxide in the initial raw materials is completely stabilized by yttrium oxide serving as a stabilizer, and the pure tetragonal structure is free from monoclinic phase; the spherical thin-wall square nano t' -YSZ powder has a spherical hollow thin-wall structure, the particle diameter D50 of the spherical is more than or equal to 60 mu m, the wall thickness is less than or equal to 6 mu m, and the average grain size is 30-50nm; the YSZ coating has high thermal shock resistance, and after the thermal barrier coating is quenched by water at 1050 ℃ for 101 times, the coating is slightly peeled off, has no phase change and is still in a pure tetragonal phase.
Description
Technical Field
The invention relates to a high-temperature long-life YSZ coating and a preparation method thereof, belonging to the field of thermal barrier coatings.
Background
7-8wt% yttria stabilized zirconia (Y 2 O 3 stabilized ZrO 2 YSZ) has low thermal conductivity, high toughness and good chemical stability, is a classical thermal barrier coating material, and is widely applied to thermal protection of hot end components of various types of aeroengines, gas turbines and the like. The long-term use temperature of the coating is below 1100 ℃ due to the limitation of phase transformation and sintering, which obviously cannot meet the requirement of continuously increasing the inlet temperature of an engine. Although a range of high temperature phase change free and sinter resistant materials have been developed, the coating life is far lower than classical YSZ coatings due to insufficient fracture toughness.
Numerous research results have demonstrated that YSZ coatings are susceptible to phase changes at high temperatures mainly due to low material phase purity. In order to improve the phase purity of the material and achieve the purposes of improving the temperature bearing capacity and prolonging the service life, the prior art develops a sol-spray pyrolysis process (SSP; patent numbers ZL201010573283.0, ZL201010533281.9, ZL201611000919.6, ZL201210358107.4, ZL 201610888017.4), breaks the bottleneck of a ' preparation and phase change ' twin technique since 60 years of use as a thermal barrier coating material, solves the problem of realizing the synchronous realization of superfine nanocrystallization and full stabilization, and realizes the full-stable tetragonal superfine nano YSZ (t ' -Zr) with uniform atomic scale 0.92 Y 0.08 O 1.96 Abbreviated as 4 YSZ) and the main performance indexes of the currently used YSZ materials are shown in table 1.
TABLE 1 Main Performance index of YSZ Material
a: a CP process; b: HS technique; c: SSP process.
This SSP process has significant advantages over current CPs and HS: (1) the uniformity of each component is high, and the thermal conductivity is low; (2) Ensure the stabilizer Y 2 O 3 Is completely dissolved in ZrO 2 In the crystal lattice, the metastable tetragonal phase t' stability of the target structure is improved, and meanwhile, the chemical instability Y is eliminated 2 O 3 Improving the chemical stability of the coating (J Achiev Mater Manuf Eng 2008,31 (2) 408-414); (3) The synthesis temperature is low, the powder grains are small, and the thermal conductivity of the coating is low; and (4) continuous production and good process stability.
The examination and verification result shows that: the use of fully stabilized tetragonal nano YSZ powder for preparing coatings by Atmospheric Plasma Spraying (APS) has significantly improved lifetime compared with existing similar materials, for example, oxidation thermal cycling at 1100 ℃, the coatings have no flaking up to 1500 times, but less than 200 times (Rare Metals 2019, https:// doi.org/10.1007/s 12598-019-01319-x) in the prior art, and furthermore, the thermal treatment at 1200 ℃ for 650h has no harmful m phase, which exceeds the engine 500h overhaul period, and more attention is paid to the fact that the thermal conductivity of the coatings is not only lower than that of the similar coatings, but also the high-temperature aging resistance (Ceram Int 2017,43,12633-12640) is mainly due to the uniform atomic scale of each component, i.e. the occurrence of phase transition is ensured, and the effect of lattice defects on thermally conductive phonon scattering is also improved. The APS coating of the fully stable tetragonal nano YSZ is sintered after long-term working at the temperature higher than 1200 ℃ and causes the porosity in the coatingDecrease, increase in Young's modulus of coating (E)>The life of the coating is reduced. At present, the use temperature of the coating is less than or equal to 1200 ℃.
If the sintering resistance is improved on the basis of the prior art, the sintering resistance of the engine is improved, the service life of the engine at 1200 ℃ is further prolonged, the service temperature is further improved, the requirement of continuously improving the inlet problem of the engine is further met, the efficiency of the engine is improved, the energy consumption is reduced, the maintenance times are reduced, and the running cost of the engine is saved.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, a high temperature long life YSZ coating is provided, which is prepared by forming a YSZ ceramic layer by spraying spherical thin wall hollow shell nano t' -YSZ powder on a bonding layer by an atmospheric plasma spraying process; the spherical thin-wall empty shell nano t' -YSZ powder is prepared from fully stable tetragonal YSZ powder through centrifugal drying and granulating.
Preferably, the bonding layer is prepared by spraying bonding layer powder on a substrate through supersonic flame spraying; the bonding layer powder is Oerlikon Metco Amdry 962 NiCrAlY, and the composition of the bonding layer powder is Ni22Cr10Al1.0Y; the matrix is M951 alloy with the diameter of 25.4mm and the thickness of 5 mm; the substrate is cleaned of oxides and oil stains using the front surface, and then sandblasted.
Preferably, the technological parameters of the atmospheric plasma spraying are as follows: 400-600A of current, 60-70V of voltage, 40-45L/min of argon flow, 6-7L/min of hydrogen flow, 100-120 mm of spraying distance, 25-35 g/min of powder feeding rate and 400-600 mm/s of gun speed.
Preferably, the preparation method of the fully stable tetragonal YSZ powder comprises the following steps: zr (NO) with purity of 99.99% 3 ) 4 ·3H 2 O and Y (NO) 3 ) 3 ·6H 2 O is used as raw material, and Zr (NO) 3 ) 4 ·3H 2 O:Y(NO 3 ) 3 ·6H 2 Preparing O=0.92:0.08 ingredients, preparing an aqueous solution with the total concentration of metal ions being 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3 hours until the solution is clear and transparent, sequentially adding additive citric acid hexahydrate and polyethylene glycol with molecular weight of 20000, wherein the adding amount of the citric acid is 160g/L, and the polyethylene glycol is 20g/L, magnetically stirring until the solution is clear and transparent, and thus preparing sol; atomizing the sol into a corundum crucible by a pressure atomization method, wherein the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃; after the sol is atomized, the corundum crucible is used forRaising the temperature to 500-900 ℃ for heat preservation for 1h, and cooling to room temperature to obtain fully-stable tetragonal YSZ powder; the fully stabilized tetragonal YSZ powder has a 100% tetragonal phase structure and an average grain size of 15-20 nm.
Preferably, the fully stabilized tetragonal YSZ powder is pre-treated by the following steps: the fully stable tetragonal YSZ powder is put into a low temperature plasma generating device for treatment, the treatment temperature of the device is controlled to be 45-70 ℃, the flow rate of oxygen is regulated to be 30-55 mL/min, the pressure is 1.5-12 Pa, the voltage is 5 kV-35 kV, the plasma treatment power is controlled to be 300-450W, and the treatment time is 2-4 min.
Preferably, the spherical thin-wall hollow nano t' -YSZ powder is prepared from fully stable tetragonal YSZ powder through centrifugal drying granulation, and the process comprises the following steps:
firstly, performing primary grinding on the fully-stabilized tetragonal YSZ powder by adopting wet ball milling;
step two, carrying out fine grinding on the slurry subjected to wet ball milling on a sand mill;
adding PVA1799 aqueous solution, n-octanol, ammonium citrate and ultrapure water into the ground slurry, and stirring until the mixture is uniform to obtain mixed slurry;
granulating the mixed slurry by adopting a centrifugal drying tower;
and fifthly, carrying out heat treatment on the particles obtained in the step four to obtain the spherical thin-wall empty shell nano t' -YSZ powder.
Preferably, in the first step, the wet ball milling is carried out until the D50 is less than or equal to 5 mu m; the mass ratio of the material, the grinding medium and the dispersing medium of the wet ball milling is 1:3 to 5:0.3 to 0.5; the grinding medium was 3Y-TZP of 99.9% chemical purity, i.e., 3mol% Y 2 O 3 Stabilized ZrO 2 Its diameter is5mm and 10mm, respectively accounting for 30%, 40% and 30%; the dispersion medium is ultrapure water, and the resistivity of the dispersion medium is 18MΩ;
in the second step, fine grinding is carried out until the D50 is less than or equal to 200nm; diameter for fine grindingThe wear rate of the 3Y-TZP zirconium beads is lower than 0.0001% in ten thousand hours; the working frequency of the sand mill is 20-40 Hz;
in the third step, the dosage of PVA1799 aqueous solution is 4-6% of the mass of the slurry; the concentration of PVA1799 water solution is 8-12 wt%; 3-4L of ultrapure water, 15-25 g of n-octanol defoamer and 4-6 g of ammonium citrate water reducer are added into each 1kg of slurry;
in the fourth step, the water evaporation capacity of the centrifugal drying tower is 5L/h, and the diameter of the mixed slurry is adoptedPumping the powder into a centrifugal drying tower, wherein the slurry inlet amount of the peristaltic pump is 70-90 mL/min, the rotating speed of a centrifugal atomizing disc is 20-25 Hz, the inlet temperature is 250-270 ℃, the outlet temperature is controlled at 110-130 ℃, and 200-400 mesh powder is sieved to be used as the heat treatment powder in the step five;
in the fifth step, the heat treatment process is as follows: heating to 300-350 ℃ at the speed of 1-2 ℃/min, preserving heat for 1-2 h, continuously heating to 480-550 ℃ at the speed of 1-2 ℃/min, preserving heat for 1-2 h, heating to 1200 ℃ at the speed of 10-15 ℃/min, and preserving heat for 1-3 h.
300～350℃，
Preferably, the spherical thin-wall hollow nano t' -YSZ powder has a spherical hollow thin-wall structure, the particle diameter D50 of the spherical is more than or equal to 60 mu m, the wall thickness is less than or equal to 6 mu m, and the average grain size is 30-50nm.
Preferably, the grain size of the YSZ coating is 110-120 nm; the coating contains a large number of holes with the size of 0.5-4.0 μm in a dispersion distribution, and the apparent density rho of the coating is 4.76g/cm 3 The porosity was 21.5%.
Preferably, the adhesive layer has an average thickness of 100 μm and the YSZ ceramic layer has an average thickness of 200 μm.
The invention at least comprises the following beneficial effects:
compared with the conventional thermal barrier coating ceramic layer, the powder and the YSZ coating prepared by the powder have outstanding substantial characteristics:
(1) Because monoclinic phase exists in the general commercial starting powder, the occurrence of the monoclinic phase not only can reduce the heat insulation effect of the YSZ coating, but also can reduce the thermal cycle life of the coating;
(2) The spherical thin-wall square nano t' -YSZ powder has a spherical hollow thin-wall structure, the particle diameter D50 of the spherical is more than or equal to 60 mu m, the wall thickness is less than or equal to 6 mu m, and the average grain size is 30-50nm;
(3) YSZ coating phase stabilization temperature: 1200 ℃ more than 1000h,1300 ℃ more than 500h,1400 ℃ more than 100h,1600 ℃ more than 30 h;
(4) YSZ coating sintering temperature resistance: > 1500 ℃;
(5) The YSZ coating has high thermal shock resistance, and after the thermal barrier coating is quenched by water at 1050 ℃ for 101 times, the coating is slightly peeled off, has no phase change and is still in a pure tetragonal phase.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an X-ray diffraction pattern of the product of example 1 according to the present invention after spray pyrolysis and heat treatment at 900℃for 1 hour; the figure also shows the standard PDF card spectrum of tetragonal zirconia (number: PDF # 48224), metco, praxair, saint-Gobain, YSZ product X-ray diffraction spectrum of the new chemical company of the university of geology of China, zichuan-style;
FIG. 2 is an X-ray diffraction pattern of the product of example 1 according to the present invention after spray pyrolysis and heat treatment at 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1200 ℃ for 1 hour;
FIG. 3 is an X-ray diffraction pattern of spherical thin-walled hollow shell nano t' -YSZ powder prepared by granulating according to example 1 of the invention; the standard PDF card map of tetragonal zirconia is also shown (number: PDF # 48224);
FIG. 4 is a surface SEM image of spherical thin-walled hollow-shell nano-t' -YSZ powder prepared according to example 1 of the invention;
FIG. 5 is a particle SEM image of spherical thin-walled hollow-shell nano-t' -YSZ powder prepared according to example 1 of the invention; thin wall SEM images;
FIG. 6 is a thin-wall SEMSEM image of a spherical thin-wall hollow nano-t' -YSZ powder prepared according to example 1 of the invention;
FIG. 7 is an X-ray diffraction pattern and SEM image of a YSZ coating prepared according to example 1 of the invention
FIGS. 8 (a) and 8 (b) are metallographic microstructures and surface macrostructures of YSZ coatings prepared according to embodiments of the invention;
FIG. 9 is an X-ray diffraction pattern of the product of the prepared YSZ coating after heat treatment at 1200 ℃ for 50 hours, 1000 hours, 1300 ℃ for 500 hours, 1400 ℃ for 100 hours, 1600 ℃ for 30 hours;
FIG. 10 is a plot of YSZ coating linear shrinkage as a function of sintering time prepared according to example 1 of the invention;
FIG. 11 is a plot of sintered coating linear shrinkage as a function of sintering time at 1400℃for example 1 and example 2;
FIG. 12 is a plot of sintered coating linear shrinkage versus sintering time for example 1 and example 2 at 1500 ℃;
FIG. 13 is a 1300 ℃ sintering pore profile (insert coating sintering 200h metallographic pore image) of a YSZ coating prepared according to an embodiment of the invention;
FIG. 14 is a macroscopic photograph of a 1050 ℃ water quenched test surface of a YSZ coating prepared according to an embodiment of the invention;
FIG. 15 is a macroscopic photograph of the coating prepared in example 2 of the present invention after 101 water quenches;
FIGS. 16 (a) and 16 (b) are metallographic images of YSZ coating as deposited and 60 cycles of 1050 ℃ water quenching prepared according to an example of the invention.
Figure 17 is an XRD pattern for a YSZ coating prepared according to an embodiment of the present invention for various times of 1050 ℃ water quench cycles.
The specific embodiment is as follows:
the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a high-temperature long-life YSZ coating is prepared by spraying spherical thin-wall hollow nano t' -YSZ powder on a bonding layer by an atmospheric plasma spraying process to form a YSZ ceramic layer; the spherical thin-wall empty shell nano t' -YSZ powder is prepared from fully stable tetragonal YSZ powder through centrifugal drying and granulating; an Atmospheric Plasma Spray (APS) device is Unicoat manufactured by Oerlikon Metco, the process parameters of which are shown in table 2:
TABLE 2
The bonding layer is prepared by spraying bonding layer powder on a substrate through ultrasonic flame spraying (HVOF) unicoat Pro-LF system preparation of Olikon Metco; the bonding layer powder is NiCrAlY with the brand Oerlikon Metco Amdry 962, and as shown in table 3, the composition of the bonding layer powder is Ni22Cr10Al1.0Y; the matrix is M951 alloy with the diameter of 25.4mm and the thickness of 5mm, the components are shown in table 4 (M951 alloy components (mass fraction/%);
TABLE 3 Table 3
| Number plate | Composition of the components | Particle size distribution (μm) | Temperature (following spray mode) |
| Amdry962 | Ni22Cr10Al1.0Y | 53～106 | ≤980℃(APS)/≤1050℃(HVOF) |
TABLE 4 Table 4
| Element(s) | Ni | W | Mo | Cr | Nb | Co | Al | C | B | Y | Other |
| Content of | Balance | 2.5-4.5 | 2.5-3.5 | 8-10 | 1.8-2.4 | 4.5-5.5 | 5.5-6.2 | 0.03-0.15 | ＜0.004 | ＜0.05 | ＜1.03 |
The preparation method of the fully stable tetragonal YSZ powder comprises the following steps: zr (NO) with purity of 99.99% 3 ) 4 ·3H 2 O and Y (NO) 3 ) 3 ·6H 2 O is used as raw material, and Zr (NO) 3 ) 4 ·3H 2 O:Y(NO 3 ) 3 ·6H 2 Preparing O=0.92:0.08 ingredients, preparing an aqueous solution with the total concentration of metal ions being 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3 hours until the solution is clear and transparent, sequentially adding additive citric acid hexahydrate and polyethylene glycol with molecular weight of 20000, wherein the adding amount of the citric acid is 160g/L, and the polyethylene glycol is 20g/L, magnetically stirring until the solution is clear and transparent, and thus preparing sol; atomizing the sol into a corundum crucible by a pressure atomization method, wherein the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃; after sol atomization is finished, the temperature of the corundum crucible is raised to 900 ℃ and kept for 1h, and then the corundum crucible is cooled to room temperature to obtain fully-stable tetragonal YSZ powder;
phase testing was performed using a multifunctional X-ray diffractometer with model X 'Pert PRO, equipped with an X' celearator super detector, manufactured by panaceae, netherlands, the X-ray being Cu target kα1, wavelength λ= 0.15406nm. Selecting (111) crystal planes according to the Shelle formula: d=0.89 λ/βcosθ, grain size 15nm; the XRD pattern is shown in figure 1;
the XRD test and analysis results shown in fig. 1 indicate that the prepared 4YSZ powder (fully stabilized tetragonal YSZ powder) of this example is compared with the tetragonal t-phase XRD standard card PDF48224#, the characteristic diffraction peaks of crystal planes of tetragonal zirconia such as (111), (002), (200), (004) and (400) are all detected, and compared with monoclinic m and cubic c-phase XRD standard cards PDF861450# and PDF821246#, there are no m and c phases, indicating that the spray pyrolysis synthesized YSZ initial raw material of this example is a pure tetragonal zirconia phase. And other domestic and foreign company products all contain m phases;
meanwhile, a comparison experiment is carried out, after sol atomization is completed, the temperature of a corundum crucible is raised to 500-1200 ℃, and after heat preservation is carried out for 1h, the corundum crucible is cooled to room temperature, so that fully-stable tetragonal YSZ powder is obtained; the XRD pattern is shown in figure 2;
in FIG. 2, the diffraction peak positions in XRD patterns are consistent in the temperature range of 500-1200 ℃, M phase is not found, and the low-temperature synthesis is carried out at 500 ℃ (the synthesis temperature of CP and HS process is 1000 ℃), which shows that the preparation method realizes non-diffusion in-situ low-temperature solid solution, Y 3+ With Zr 4+ The uniformity between the two is obviously superior to other preparation methods. The product synthesized by the novel process is T' - (Zr) 0.92 Y 0.08 )O 1.96 This demonstrates that the new process enables precise control of the YSZ component.
The spherical thin-wall empty shell nano t' -YSZ powder is prepared from fully stable tetragonal YSZ powder through centrifugal drying and granulating, and the process comprises the following steps:
firstly, performing primary grinding on the fully-stabilized tetragonal YSZ powder by adopting wet ball milling; the mass ratio of the material, the grinding medium and the dispersing medium of the wet ball milling is 1:3 to 5:0.3 to 0.5; the grinding medium was 3Y-TZP (3 mol% Y) of 99.9% chemical purity 2 O 3 Stabilized ZrO 2 Produced by the eastern zirconium industry), its diameter5mm and 10mm, respectively accounting for 30%, 40% and 30%; the dispersion medium is ultrapure water (resistivity=18mΩ), ball milling is carried out until D50 is less than or equal to 5 μm, and the fineness of the slurry is tested by a laser particle size analyzer;
step two, slurry after wet ball milling is carried outFine grinding is carried out on a sand mill; diameter for fine grindingThe wear rate of the 3Y-TZP zirconium beads is lower than 0.0001% in ten thousand hours; the effective volume of the sand mill is 1L, the working frequency f=20-40 Hz, the grinding time of the average 1L primary grinding slurry is used for controlling the fineness of the fine grinding slurry, the grinding is carried out until the D50 is less than or equal to 200nm, and the fineness of the slurry is tested by adopting a laser granularity analyzer;
adding PVA1799 aqueous solution, n-octanol, ammonium citrate and ultrapure water into the ground slurry, and stirring until the mixture is uniform to obtain mixed slurry; the dosage of PVA1799 aqueous solution is 5% of the slurry mass; the concentration of the PVA1799 aqueous solution was 10wt%; 3.5L of ultrapure water, 20g of n-octanol defoamer and 5g of ammonium citrate water reducer are added into 1kg of slurry;
granulating the mixed slurry by adopting a centrifugal drying tower; the water evaporation capacity of the centrifugal drying tower is 5L/h, and the diameter of the mixed slurry is adoptedPumping the powder into a centrifugal drying tower, wherein the slurry inlet amount is 80mL/min, the rotating speed of a centrifugal atomizing disc is 22Hz, the inlet temperature is 260 ℃, the outlet temperature is controlled at 120 ℃, and 200-400 meshes of powder is sieved to be used as the heat treatment powder in the step five;
step five, carrying out heat treatment on the particles obtained in the step four to obtain spherical thin-wall empty shell nano t' -YSZ powder; the heat treatment process comprises the following steps: heating to 300 ℃ at a speed of 1 ℃/min, preserving heat for 1.5h, continuously heating to 500 ℃ at a speed of 1 ℃/min, preserving heat for 1.5h, then heating to 1200 ℃ at a speed of 10 ℃/min, preserving heat for 2h, and finally cooling to room temperature along with a furnace, thereby preparing anti-sintering spherical thin-wall empty shell nano t' -YSZ powder;
phase testing was performed using a multifunctional X-ray diffractometer with model X 'Pert PRO, equipped with an X' celearator super detector, manufactured by panaceae, netherlands, the X-ray being Cu target kα1, wavelength λ= 0.15406nm. The XRD pattern is shown in figure 3. The particle size of the spherical thin-walled hollow nano t' -YSZ powder material is 14-105 μm as observed by a field emission scanning electron microscope (FETS) with the model of Ultra 55 manufactured by Chuiss, germany, and SEM images are shown in figures 4-6.
As shown in XRD test and analysis results shown in FIG. 3, the prepared spherical thin-wall empty shell nano t' -YSZ powder of the embodiment is compared with a tetragonal t-phase XRD standard card PDF48224#, characteristic diffraction peaks of crystal faces such as (111), (002), (200), (004) and (400) of tetragonal zirconia are detected, and the powder is compared with monoclinic m and cubic c-phase XRD standard cards PDF861450# and PDF821246#, and no m and c phases are shown, so that the powder synthesized by centrifugal drying granulation of the embodiment is a pure tetragonal zirconia phase. SEM results show that the powder is spherical and has higher sphericity, the interior of the powder particles is of a cavity structure, the shell wall is compact and has uniform thickness (4-6 mu m), and the inner and outer surfaces are smooth.
High temperature long life YSZ coating structural characterization of this example:
phase testing was performed using a multifunctional X-ray diffractometer with model X 'Pert PRO, equipped with an X' celearator super detector, manufactured by panaceae, netherlands, the X-ray being Cu target kα1, wavelength λ= 0.15406nm. The XRD pattern is shown in FIG. 7 (a). The microstructure of the coating was observed by means of a field emission scanning electron microscope, model Ultra 55, manufactured by zeiss, germany, see fig. 7 (b) for SEM images. The coating is still in the t' -YSZ phase, and the (111) plane is selected according to the scherrer formula: d=0.89 λ/βcosθ, coating grain size 114nm; the coating has no unmelted area and no interlayer interface, contains a large number of holes with a dispersion distribution size ranging from 0.5 to 4.0 μm, and has an apparent density ρ of 4.76g/cm calculated from the mass and geometric volume of the coating 3 Compared with the theoretical density of the material (6.07 g/cm 3 ) The porosity of the coating was low, i.e. 21.5%.
Microstructure analysis was performed using a metallographic microscope model DM2700M manufactured by Leica, germany. The metallographic microstructure and macroscopic view of the prepared NiCrAlY bonding layer and YSZ ceramic layer are shown in fig. 8 (a) and (b), the average thickness is 100 μm and 200 μm respectively, the interfaces between the ceramic layer and the bonding layer and between the bonding layer and the matrix alloy are clear, the bonding is good, and a large number of pores which are uniformly distributed are formed in the ceramic layer without cracks.
High temperature phase stability of the high temperature long life YSZ coating structure of this embodiment:
and (3) placing the prepared coating into a high-purity alumina crucible, placing the high-purity alumina crucible under a thermocouple in a program-controlled high-temperature furnace for heat treatment, wherein the heat treatment temperature is 1200 ℃,1300 ℃,1400 ℃ and 1600 ℃, the heat treatment time is 1000h, 300h, 100h and 30h respectively, the heating rate is 3.5 ℃/min, the temperature is reduced to 800 ℃ at the rate of 2 ℃/min, and then the furnace is cooled to room temperature. XRD results are shown in fig. 9, where no m-phase diffraction peak was found at both 2θ=28.2° and 31.2 ° positions. On the basis of earlier work, the APS coating prepared from the fully-stable nano YSZ powder can reach 1200 ℃ for 650 hours without m phases (Ceram Int 2017,43,12633-12640, patent number: CN 107815633A). The literature reported for APS coatings has 11mol% m-phase (Adv in Ceram1981 (3) 241-253;J Therm Spray Technol2001,10 (3) 497-501) after 100-400 hours calcination at 1473K, and 3mol% m-phase (J Am Ceram Soc 2000,83 (4) 904-910) after 200 hours calcination at 1473K for YSZ coatings prepared by electron beam physical vapor deposition. This shows that the high temperature phase stability of the YSZ coating prepared by the invention is better, the service temperature of the YSZ coating can be increased from 1100 ℃ to 1200 ℃ or even higher, and the application temperature of the high Wen Reduan part protective coating can be further increased.
Example 2:
the preparation method of the fully stable tetragonal YSZ powder comprises the following steps: zr (NO) with purity of 99.99% 3 ) 4 ·3H 2 O and Y (NO) 3 ) 3 ·6H 2 O is used as raw material, and Zr (NO) 3 ) 4 ·3H 2 O:Y(NO 3 ) 3 ·6H 2 Preparing O=0.92:0.08 ingredients, preparing an aqueous solution with the total concentration of metal ions being 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3 hours until the solution is clear and transparent, sequentially adding additive citric acid hexahydrate and polyethylene glycol with molecular weight of 20000, wherein the adding amount of the citric acid is 160g/L, and the polyethylene glycol is 20g/L, magnetically stirring until the solution is clear and transparent, and thus preparing sol; atomizing the sol into a corundum crucible by a pressure atomization method, wherein the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃; after sol atomization, the corundum crucible temperature is raised to 900 ℃ and kept for 1h, and then cooled to room temperature to obtainFully stabilized tetragonal YSZ powder; placing the fully stable tetragonal YSZ powder into a low-temperature plasma generating device for treatment, controlling the treatment temperature of the device to be 60 ℃, adjusting the flow rate of oxygen to be 45mL/min, controlling the pressure to be 3Pa, controlling the voltage to be 15kV, controlling the plasma treatment power to be 300W and controlling the treatment time to be 3min;
exactly the same process parameters and procedure as in example 1.
Anti-sintering properties of high temperature long life YSZ coating structures of example 1 and example 2:
and sintering the APS prepared coating sample at 1200 ℃,1300 ℃,1400 ℃ and 1500 ℃ for heat treatment for 100h, 200h, 100h and 100h respectively, wherein the heating rate is 3.5 ℃/min, cooling to 800 ℃ at the rate of 2 ℃/min, cooling to room temperature along with a furnace, and testing the density, linear shrinkage, porosity and microscopic morphology of the sintered sample at different temperatures and times.
(1) Linear shrinkage of coating sintering
According to epsilon=Δl/L 0 ×100％＝(L 0 -L)/L 0 X100% calculation of the coating sintering Linear shrinkage, L 0 And L represents the size of the coating before and after sintering, respectively.
(2) Coating sintering porosity
According to the following formulaRelative density method for calculating macroscopic sintering porosity, ρ and ρ of coating 0 Apparent and theoretical density (g/cm) 3 )。
In addition, the number of the coating thickness parallel section metallographic microstructure test areas is not less than 5 in sequence, and the microscopic porosity of the coating is calculated by statistics according to the ratio of the black-white binary porosity to the coating area after metallographic microscopic image processing, and the average value is calculated.
The linear shrinkage of the sintered coating at 1200 ℃,1300 ℃,1400 ℃ and 1500 ℃ as a function of sintering time is shown in FIG. 10. The shrinkage of the coating was very small (< 0.5%) over all sintering temperature ranges described above. FIG. 11 is a plot of the linear shrinkage of the sintered coatings as a function of sintering time at 1400℃for example 1 and example 2. FIG. 12 is a plot of the linear shrinkage of the sintered coatings as a function of sintering time at 1500℃for example 1 and example 2. The linear shrinkage of the coating prepared in example 2 was smaller than that of the coating prepared in example 1; the sintered porosity of the coatings at 1300 ℃ was tested by the relative density method and plotted as a function of time as in fig. 13 (inset is 200h metallographic phase x 100). The porosity of the coating is reduced by 1% from 22% in the initial state within the range of 0-200 h, the metallographic image shows that the coating contains a large number of pores which are distributed in a dispersed way, and the porosity of the metallographic image is 20.5% according to statistics by a black-white binary method and is consistent with the value measured by the previous relative density method. The YSZ coating reported in the literature is easy to sinter at temperatures above 1200 ℃, such as 1510 ℃ for 24 hours, and the linear shrinkage is 3.7 percent (Surf Coat Technol 1987,32 (1-4) 227-236); the material is sintered at 1300 ℃ for 100 hours, the linear shrinkage rate is 1.02 percent, and the porosity is reduced by 23.6 percent (Surf Coat Technol 2009,203,1069-1074) from 19.1 percent in the initial state. The spherical thin-wall hollow-shell tetragonal nano t' -YSZ powder prepared by the invention has a large number of closed pores in the coating, and the closed pores play a key role in improving the high-temperature sintering resistance of the coating. Therefore, the YSZ coating prepared by the invention solves the phase change and sintering problems which limit the service temperature and service life of the coating.
Thermal shock resistance of high temperature long life YSZ coating structures of example 1 and example 2:
the APS prepared coating sample is checked according to the thermal shock performance test method of aviation industry standard HB 7269-96. And (3) placing the sprayed coating sample into a high-temperature furnace, preserving the temperature at 1050 ℃ for 10min, taking out the sample, and rapidly putting the sample into deionized water at 20+/-5 ℃ for quenching for 5min. And (3) repeatedly carrying out the steps, recording the times of thermal shock water quenching, and observing the conditions of cracking, peeling or flaking and the like on the surface of the coating.
Macroscopic photographs of the coated samples with the substrate and metal tie layer after 10, 30, 70, 90, 101 water quenches are shown in fig. 14, respectively. The results show that the coating is quenched by water for 101 times, only a part of edges and the center of the sample are slightly peeled off, and the whole is relatively intact. Fig. 15 is a macroscopic photograph of the coating prepared in example 2 after 101 water quenches, with substantially no flaking and intact overall. TGO generation between the ceramic layer and the bonding layer is not found in the metallographic microstructure before and after the water quenching thermal cycle of the coating (figure 16), the porosity is basically unchanged, and the porosity is reduced by-1% from 21.5% of the initial state; XRD detection results (fig. 17) showed that the coating remained in a pure t' -YSZ phase structure before and after water quenching. The thermal shock resistance of the YSZ coating prepared by the invention is more than 16 times of that required in aviation industry standard HB7269-96 (coating peeling after water quenching is repeated for 6 times), and more than 3 times of that of the existing commercial YSZ powder (coating peeling after water quenching is repeated for 30 times). This shows that the present invention breaks the phase transition and sintering problems of the YSZ coating by advanced preparation techniques, and has realized the preparation of long-life YSZ coatings.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (6)
1. A high-temperature long-life YSZ coating is characterized in that the YSZ coating is prepared by forming a YSZ ceramic layer on a bonding layer by spraying spherical thin-wall hollow shell nano t' -YSZ powder through an atmospheric plasma spraying process;
the spherical thin-wall empty shell nano t' -YSZ powder is prepared from fully stable tetragonal YSZ powder through centrifugal drying and granulating, and the process comprises the following steps:
firstly, performing primary grinding on the fully-stabilized tetragonal YSZ powder by adopting wet ball milling; in the first step, ball milling is carried out by a wet method until D50 is less than or equal to 5 mu m; the mass ratio of the material, the grinding medium and the dispersing medium of the wet ball milling is 1: 3-5: 0.3 to 0.5; the grinding medium was 3Y-TZP of 99.9% chemical purity, i.e., 3mol% Y 2 O 3 Stabilized ZrO 2 The diameter phi=3 mm, 5mm and 10mm, and the ratios of the diameter phi to the diameter phi are 30%, 40% and 30%; the dispersion medium is ultrapure water, and the resistivity of the dispersion medium is 18MΩ;
step two, carrying out fine grinding on the slurry subjected to wet ball milling on a sand mill; in the second step, fine grinding is carried out until D50 is less than or equal to 200 and nm; the 3Y-TZP zirconium beads with the diameter phi=0.1-0.3 mm are adopted for fine grinding, and the ten thousand-hour wear rate is lower than 0.0001%; the working frequency of the sand mill is 20-40 Hz;
adding PVA1799 aqueous solution, n-octanol, ammonium citrate and ultrapure water into the ground slurry, and stirring until the mixture is uniform to obtain mixed slurry; in the third step, the dosage of PVA1799 aqueous solution is 4-6% of the mass of the slurry; the concentration of the PVA1799 aqueous solution is 8-12wt%; 3-4L of ultrapure water, 15-25 g of n-octanol defoamer and 4-6 g of ammonium citrate water reducer are added into each 1kg of slurry;
granulating the mixed slurry by adopting a centrifugal drying tower; in the fourth step, the water evaporation capacity of the centrifugal drying tower is 5L/h, the mixed slurry is pumped into the centrifugal drying tower by adopting a peristaltic pump with the diameter phi=11 mm, the slurry inlet capacity is 70-90 mL/min, the rotating speed of a centrifugal atomizing disc is 20-25 Hz, the inlet temperature is 250-270 ℃, the outlet temperature is controlled at 110-130 ℃, and 200-400 mesh powder is sieved to be used as the heat treatment powder in the fifth step;
step five, carrying out heat treatment on the particles obtained in the step four to obtain spherical thin-wall empty shell nano t' -YSZ powder; in the fifth step, the heat treatment process is as follows: heating to 300-350 ℃ at a speed of 1-2 ℃/min, preserving heat for 1-2 h, continuously heating to 480-550 ℃ at a speed of 1-2 ℃/min, preserving heat for 1-2 h, heating to 1200 ℃ at a speed of 10-15 ℃/min, and preserving heat for 1-3 h;
the preparation method of the fully stable tetragonal YSZ powder comprises the following steps: zr (NO) with purity of 99.99% 3 ) 4 ·3H 2 O and Y (NO) 3 ) 3 ·6H 2 O is used as raw material, and Zr (NO) 3 ) 4 ·3H 2 O:Y(NO 3 ) 3 ·6H 2 Preparing O=0.92:0.08 ingredients, preparing an aqueous solution with the total concentration of metal ions being 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3 hours until the solution is clear and transparent, sequentially adding additive citric acid hexahydrate and polyethylene glycol with molecular weight of 20000, wherein the adding amount of the citric acid is 160g/L, and the polyethylene glycol is 20g/L, magnetically stirring until the solution is clear and transparent, and thus preparing sol; atomizing the sol into a corundum crucible by a pressure atomization method, wherein the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃; after the sol atomization is finishedRaising the temperature of the corundum crucible to 500-900 ℃, preserving heat for 1h, and cooling to room temperature to obtain fully-stable tetragonal YSZ powder; the fully stable tetragonal YSZ powder is of a 100% tetragonal phase structure, and the average grain size of the fully stable tetragonal YSZ powder is 15-20 nm;
the preparation method comprises the following steps of: and (3) placing the fully-stabilized tetragonal YSZ powder into a low-temperature plasma generating device for treatment, wherein the treatment temperature of the device is controlled to be 45-70 ℃, the flow of oxygen is regulated to be 30-55 mL/min, the pressure is 1.5-12 Pa, the voltage is 5 kV-35 kV, the plasma treatment power is controlled to be 300-450W, and the treatment time is 2-4 min.
2. The high temperature long life YSZ coating of claim 1, wherein the tie layer is prepared from tie layer powder by spray-coating with supersonic flame on a substrate; the bonding layer powder is Oerlikon Metco Amdry 962 NiCrAlY, and the composition of the bonding layer powder is Ni22Cr10Al1.0Y; the matrix is an M951 alloy with the diameter of 25.4mm and the thickness of 5 mm; the substrate is cleaned of oxides and oil stains using the front surface, and then sandblasted.
3. The high temperature long life YSZ coating of claim 1 wherein the process parameters of the atmospheric plasma spray are: the current is 400-600A, the voltage is 60-70V, the argon flow is 40-45 liters/min, the hydrogen flow is 6-7 liters/min, the spraying distance is 100-120 mm, the powder feeding rate is 25-35 g/min, and the gun speed is 400-600 mm/s.
4. The high temperature long life YSZ coating of claim 1, wherein the spherical thin wall hollow shell nano t' -YSZ powder has a spherical hollow shell thin wall structure, the spherical particle size D50 is not less than 60 μm, the wall thickness is not more than 6 μm, and the average grain size is 30-50nm.
5. The high temperature long life YSZ coating of claim 1, wherein the YSZ coating grain size is 110-120 nm; the coating contains a large number of holes with the size of 0.5-4.0 μm in a dispersion distribution, and the apparent density rho of the coating is 4.76g/cm 3 The porosity was 21.5%.
6. The high temperature long life YSZ coating of claim 1 wherein the average thickness of the tie layer is 100 μm and the average thickness of the YSZ ceramic layer is 200 μm.
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