CN116023136B - Nano-structure rare earth hafnate ceramic powder feed for thermal spraying and preparation method and application thereof - Google Patents
Nano-structure rare earth hafnate ceramic powder feed for thermal spraying and preparation method and application thereof Download PDFInfo
- Publication number
- CN116023136B CN116023136B CN202310055882.0A CN202310055882A CN116023136B CN 116023136 B CN116023136 B CN 116023136B CN 202310055882 A CN202310055882 A CN 202310055882A CN 116023136 B CN116023136 B CN 116023136B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- hafnate
- oxide
- ceramic powder
- powder feed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 149
- 239000000843 powder Substances 0.000 title claims abstract description 128
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 80
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 80
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 44
- 238000007751 thermal spraying Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 230000007613 environmental effect Effects 0.000 claims abstract description 12
- 230000004888 barrier function Effects 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims description 65
- 238000001694 spray drying Methods 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 39
- 238000005245 sintering Methods 0.000 claims description 36
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 35
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 27
- 238000000498 ball milling Methods 0.000 claims description 23
- 238000005336 cracking Methods 0.000 claims description 23
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 23
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 21
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 21
- 229940075624 ytterbium oxide Drugs 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000002159 nanocrystal Substances 0.000 claims description 9
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 6
- 229940075613 gadolinium oxide Drugs 0.000 claims description 6
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 6
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 4
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 4
- 229910003443 lutetium oxide Inorganic materials 0.000 claims description 3
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 51
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 238000000227 grinding Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- 238000005524 ceramic coating Methods 0.000 description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 5
- 229910052765 Lutetium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- -1 Calcium Magnesium Aluminum Chemical compound 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000012720 thermal barrier coating Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a nano-structure rare earth hafnate ceramic powder feed for thermal spraying, a preparation method and application thereof, belonging to the technical field of ceramic materials. The rare earth hafnate ceramic powder provided by the invention has the advantages of high feeding sphericity, uniform granularity distribution and good fluidity, and can meet the application requirements of heat/environmental barrier coatings.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a nano-structure rare earth hafnate ceramic powder feed for thermal spraying and a preparation method and application thereof.
Background
The thermal/environmental barrier coating is used for further improving the service temperature of the silicon carbide ceramic matrix composite by reducing the surface temperature of the intermediate layer on the basis of the environmental barrier coating; research has found that by CaO, mgO, al 2 O 3 And SiO 2 The environmental deposits of the composition have a great influence on the lifetime of the thermal barrier coating. The rare earth zirconate material has the advantages of lower heat conductivity, higher melting point and better Calcium Magnesium Aluminum Silicate (CMAS) corrosion resistance, and becomes the main material of the top heat insulation layer of the heat/environment barrier coating at the present stage.
However, the rare earth zirconate material has poor fracture toughness, which results in a thermal barrier coating prepared from the rare earth zirconate material having a shorter thermal cycle life; accordingly, there is an urgent need to provide a coating material having good fracture toughness to improve damage tolerance and thermal cycle life of the coating.
Disclosure of Invention
Aiming at one or more technical problems in the prior art, the invention provides a nano-structure rare earth hafnate ceramic powder feed for thermal spraying, and a preparation method and application thereof.
The invention provides a nano-structured rare earth hafnate ceramic powder feed for thermal spraying, which consists of nanocrystals.
Preferably, the grain size of the rare earth hafnate ceramic powder feed is 10-40 mu m; and/or
The grain size of the nanocrystalline is 1-30 nm.
The invention provides a preparation method of the nano-structure rare earth hafnate ceramic powder feed for thermal spraying, which comprises the following steps:
s1, performing ball milling and mixing on rare earth oxide, hafnium oxide, a solvent and a binder to obtain slurry;
s2, drying, loose sintering the slurry to obtain a rare earth hafnate ceramic block;
s3, ball-milling, mixing and drying the rare earth hafnate ceramic block, the solvent and the binder to obtain spherical ceramic powder;
s4, cracking and discharging glue from the spherical ceramic powder to obtain the rare earth hafnate ceramic powder feed.
Preferably, in step S1, the molar ratio of rare earth oxide to hafnium oxide is 2:3; preferably, the rare earth oxide is one of scandium oxide, yttrium oxide, ytterbium oxide, gadolinium oxide, holmium oxide, erbium oxide and lutetium oxide.
Preferably, in step S1, the solvent is used in an amount of (1/2 to 2/3) of the mass of the slurry; and/or
The mass of the binder is 0.2-0.5% of the total mass of the rare earth oxide and the hafnium oxide.
Preferably, in step S1, the rare earth oxide has a particle size of 15 to 40nm; and/or
The grain size of the hafnium oxide is 30-50 nm.
Preferably, in the step S2, the loose sintering is carried out at a temperature rising rate of 5-10 ℃/min for 1-2 hours before 500-750 ℃, and then sintering is carried out at 1450-1600 ℃ for 2-4 hours; and/or
In the step S4, the cracking and glue discharging is carried out for 1 to 3 hours at the temperature of 500 to 750 ℃.
Preferably, in step S1 and step S3, the solvent is one of deionized water and ethanol; the binder is polyvinyl alcohol; and/or
In the step S2 and the step S3, the drying is spray drying, the feeding rate of the spray drying is 10-60 mL/min, the inlet temperature is 190-230 ℃, and the outlet temperature is 90-110 ℃.
Preferably, in step S3, the mass ratio of the solvent to the rare earth hafnate ceramic block is (1-2): 1; and/or
The usage amount of the binder is 0.5-5% of the mass of the rare earth hafnate ceramic block.
The invention provides in a third aspect the use of the nanostructured rare earth hafnate ceramic powder feed for thermal spraying according to the first aspect in the field of thermal/environmental barrier coatings.
Compared with the prior art, the invention has at least the following beneficial effects:
the rare earth hafnate ceramic powder with the nano structure provided by the invention has the advantages of high feeding sphericity, uniform granularity distribution and good fluidity, and can be used for preparing thermal/environmental barrier coatings by thermal spraying.
According to the invention, the nano structure is introduced into the rare earth hafnate ceramic powder feed, so that the fracture toughness and damage tolerance of the nano ceramic coating obtained by spraying can be improved, the comprehensive performance of the coating is further improved, the coating still maintains high stability at high temperature, and the thermal cycle life of the coating is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a SEM topography (10 μm) of an ytterbium hafnate feed with nanostructures provided in example 1 of the invention;
FIG. 2 is a SEM cross-sectional view (10 μm) of an ytterbium hafnate feed with nanostructures provided by example 1 of the invention;
FIG. 3 is a SEM topography (20 μm) of an ytterbium hafnate feed with nanostructures as provided in example 1 of the invention;
FIG. 4 is an XRD pattern for ytterbium hafnate feed with nanostructure provided in example 1 of the present invention;
FIG. 5 is an SEM image of the nanocrystalline grains in an ytterbium hafnate feed with nanostructures provided in example 1 of the invention;
FIG. 6 is a diffraction pattern of nanocrystals in ytterbium hafnate feed with nanostructures provided in example 1 of the invention;
FIG. 7 is an EDS image of the distribution of constituent elements of nanocrystalline grains in ytterbium hafnate feedstock with nanostructures provided in example 1 of the invention;
FIG. 8 is a SEM topography (50 μm) of an ytterbium hafnate feed with nanostructures provided by example 1 of the invention;
FIG. 9 is a graph showing the particle size distribution of the ytterbium hafnate feedstock obtained by statistics of the particle size distribution of the ytterbium hafnate feedstock of FIG. 8;
FIG. 10 is a physical diagram of ytterbium hafnate ceramic block provided in example 1 of the present invention;
FIG. 11 is a TG-DSC curve of ytterbium hafnate ceramic block provided in example 1 of the present invention;
fig. 12 is an SEM morphology of ytterbium hafnate ceramic powder provided in comparative example 5 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments described below will be clearly and completely described in conjunction with the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention, and all other embodiments obtained by persons of ordinary skill in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
The invention provides a nano-structured rare earth hafnate ceramic powder feed for thermal spraying, which consists of nanocrystals.
The rare earth hafnate ceramic powder feed is a spherical feed with a nano structure, wherein the nano structure refers to that the size of crystal particles in nanocrystals forming the rare earth hafnate ceramic powder feed is nano-scale.
Compared with rare earth hafnate materials, the rare earth hafnate material has lower heat conductivity and thermal expansion coefficient, is more suitable for being used as the top layer of a thermal/environmental barrier coating, and has fluorite structure, and the rare earth hafnate reacts with Calcium Magnesium Aluminum Silicate (CMAS) at high temperature to generate an apatite phase, so that the rare earth hafnate material has excellent environmental corrosion resistance.
The rare earth hafnate ceramic powder with the nano structure provided by the invention has the advantages of high feeding sphericity, uniform granularity distribution and good fluidity, and can be used for preparing thermal/environmental barrier coatings by thermal spraying.
According to the invention, the nano structure is introduced into the rare earth hafnate ceramic powder feed, so that the fracture toughness and damage tolerance of the nano ceramic coating obtained by spraying can be improved, the comprehensive performance of the coating is further improved, the coating still maintains high stability at high temperature, and the thermal cycle life of the coating is prolonged.
According to some preferred embodiments, the rare earth hafnate ceramic powder feed has a particle size of 10 to 40 μm (e.g., may be 10 to 15 μm, 15 to 20 μm, 20 to 25 μm, 25 to 30 μm, 30 to 35 μm, or 35 to 40 μm); the grain diameter of the rare earth hafnate ceramic powder feed is controlled in the range, so that the obtained sprayed nano ceramic coating with uniform thickness, high density and high strength can be ensured; if the particle size is too large, the density and strength of the nano ceramic coating can be reduced. And/or
The size of the crystal grains of the nanocrystals is 1 to 50nm (for example, 10nm to 15nm, 15 to 20nm, 20 to 25nm, 25 to 30nm, 30 to 35nm, 35 to 40nm, 40 to 45nm, or 45 to 50nm may be used).
The invention controls the grain size in the rare earth hafnate ceramic powder feed in the range, can effectively improve the fracture toughness and damage tolerance of the nano ceramic coating, and prolongs the service life of the coating.
The invention provides a preparation method of the nano-structure rare earth hafnate ceramic powder feed for thermal spraying, which comprises the following steps:
s1, performing ball milling and mixing on rare earth oxide, hafnium oxide, a solvent and a binder to obtain slurry;
s2, drying, loose sintering the slurry to obtain a rare earth hafnate ceramic block;
s3, ball-milling, mixing and drying the rare earth hafnate ceramic block, the solvent and the binder to obtain spherical ceramic powder;
s4, cracking and discharging glue from the spherical ceramic powder to obtain the rare earth hafnate ceramic powder feed.
The invention takes nano rare earth oxide and nano hafnium oxide as raw materials, firstly adopts solid phase sintering to prepare rare earth hafnate ceramic blocks with nano structures, then adopts spray granulation to obtain spherical ceramic powder, and finally obtains rare earth hafnate ceramic powder feed with nano structures through cracking and glue discharging; the preparation method is simple, the atomic utilization rate is high, the spherical rare earth hafnate ceramic powder feed with the nano structure, which has uniform particle size distribution, good fluidity and high stability, can be prepared, and can meet the requirements of heat/environmental barrier coatings.
According to some preferred embodiments, in step S1, the molar ratio of rare earth oxide to hafnium oxide is 2:3; preferably, the rare earth oxide is one of scandium oxide, yttrium oxide, ytterbium oxide, gadolinium oxide, holmium oxide, erbium oxide and lutetium oxideA kind of module is assembled in the module and the module is assembled in the module. The invention can ensure that the rare earth hafnate RE with high purity can be obtained by controlling the mol ratio of the rare earth oxide to the hafnium oxide to be 2:3 4 Hf 3 O 12 Wherein RE is one of scandium (Sc), yttrium (Y), ytterbium (Yb), gadolinium (Gd), holmium (Ho), erbium (Er) and lutetium (Lu); the purity of the rare earth oxide and hafnate is greater than 99%.
According to some preferred embodiments, in step S1, the solvent is used in an amount of (1/2-2/3) of the mass of the slurry; the invention can obtain the evenly mixed slurry by controlling the solvent dosage in the range.
According to some preferred embodiments, in step S1, the mass of the binder is 0.2 to 0.5% (e.g., may be 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%) of the total mass of the rare earth oxide and hafnium oxide. The inventor finds that if no binder is added, the obtained slurry is dried, loose and sintered to form a compact rare earth hafnate ceramic block, and in the subsequent ball milling process, longer ball milling time is needed, and ceramic powder with uniform particle size is difficult to obtain; therefore, the invention can lead the obtained slurry to obtain spherical slurry powder after spray drying by introducing the binder with the dosage, the spherical slurry powder is loose and sintered to obtain relatively loose rare earth hafnate ceramic blocks, the ceramic powder with uniform particle size is easier to ball mill, and then the spherical ceramic powder with uniform particle size is obtained through spray granulation.
The ball-to-material ratio of ball-milling mixture in step S1 and step S3 of the present invention is (3 to 5): 1 (for example, may be 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1 or 5:1).
According to some preferred embodiments, in step S1, the rare earth oxide has a particle size of 15 to 40nm (for example, may be 15 to 20nm, 20 to 25nm, 25 to 30nm, 30 to 35nm or 35 to 40 nm); and/or
The hafnium oxide has a particle size of 30 to 50nm (for example, 30 to 35nm, 35 to 40nm, or 45 to 50 nm).
The invention selects nano-sized rare earth oxide and hafnium oxide as raw materials to prepare rare earth hafnate ceramic powder feed, so as to ensure that the rare earth hafnate ceramic powder feed with nano structure composed of nano crystals is obtained; the grain sizes of rare earth oxide and hafnium oxide are controlled in the range, so that the grain size of the nanocrystalline in the obtained rare earth hafnate ceramic powder feed is ensured to be 1-50 nm.
According to some preferred embodiments, in step S2, the loose sintering is performed at a temperature increase rate of 5-10 ℃/min (e.g., may be 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, or 10 ℃/min), prior to 500-750 ℃ (e.g., may be 500 ℃, 520 ℃, 540 ℃, 550 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, 650 ℃, 660 ℃, 680 ℃, DEG C, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, 650 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, or 750 ℃) (e.g., may be 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, or 2 h) and then sintered at 1450-1600 ℃ (e.g., may be 1450 ℃, 1460 ℃, 1470 ℃, 1480 ℃, 1490 ℃, 1500 ℃, 1510 ℃, 1520 ℃, 1530 ℃, 1540 ℃, 1550 ℃, 1560 ℃, 1570 ℃, 1580 ℃, 1590 ℃, or 1600 ℃) for 2-4 h (e.g., may be 2h, 2.2h, 2.5h, 2.6h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, or 4 h).
The loose sintering comprises two stages, wherein the first stage is to keep the temperature at 500-750 ℃ for 1-2 h, and the stage is mainly used for firstly removing the binder in the spherical slurry powder so as to ensure that the second stage is to sinter at 1450-1600 ℃ for 2-4 h, thus obtaining the rare earth hafnate ceramic block with high purity.
To determine the sintering temperature range, the inventors have determined the TG-DSC curve of a rare earth hafnate ceramic block (as in fig. 11) and found that an exothermic peak occurs at 1306.07 ℃, indicating that the sintering temperature for preparing the rare earth hafnate ceramic block must be greater than 1306 ℃. In order to ensure that the rare earth hafnate ceramic block with high purity is obtained in a short time, the sintering temperature is controlled in the range; if the sintering temperature is too low (lower than 1306 ℃), the rare earth hafnate ceramic block cannot be obtained through reaction; the too high temperature can cause the oversized crystal grains in the rare earth hafnate ceramic block, and the rare earth hafnate ceramic powder with the nano structure can not be obtained.
Further, the sintering time is controlled in the range, so that the rare earth oxide and the hafnium oxide can be ensured to completely react, and the grain size of grains in the obtained rare earth hafnate ceramic powder can be ensured to be 1-30 nm; if the sintering time is too short, the rare earth oxide and hafnium oxide react incompletely, and high-purity rare earth hafnate ceramic cannot be obtained; if the sintering time is too long, the crystal grains are too large, and the rare earth hafnate ceramic powder feed with the nano structure cannot be obtained; in the sintering temperature and time range, the size of the crystal grains can be adjusted by adjusting the sintering temperature and the sintering time; the growth of crystal grains can be promoted by properly increasing the sintering temperature or prolonging the sintering time; the specific sintering temperature and time can be adjusted according to actual conditions.
According to some preferred embodiments, in step S4, the splitting and draining is performed at 500-750 ℃ (e.g., 500 ℃, 520 ℃, 540 ℃, 550 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, 650 ℃, 660 ℃, 680 ℃, c, 550 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, 650 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, or 750 ℃), for 1-3 hours (e.g., 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, or 3 h).
According to the invention, the binder in the spherical ceramic powder is removed through cracking and glue discharging, and the temperature of cracking and glue discharging is controlled in the range, so that the binder in the spherical ceramic powder is removed on the basis that the whole morphology of the spherical ceramic powder is not influenced, and the nano rare earth hafnate ceramic powder feed with high sphericity, good fluidity and high purity is obtained; if the temperature is too low, the binder cannot be smoothly discharged; if the temperature is too high, the morphology of the nano rare earth hafnate ceramic powder feed is influenced, so that the sphericity of the feed is reduced and the fluidity is deteriorated.
According to some preferred embodiments, in step S1 and step S3, the solvent is one of deionized water and ethanol; the binder is polyvinyl alcohol.
According to some preferred embodiments, in step S2 and step S3, the drying is spray drying, the spray drying is performed at a feed rate of 10 to 60mL/min (e.g., 10mL/min, 15mL/min, 20mL/min, 25mL/min, 30mL/min, 35mL/min, 40mL/min, 45mL/min, 50mL/min, 55mL/min, or 60 mL/min), an inlet temperature of 190 to 230 ℃ (e.g., 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, or 230 ℃) and an outlet temperature of 90 to 110 ℃ (e.g., 90 ℃, 95 ℃, 100 ℃, 105 ℃, or 110 ℃). In the invention, in the step S2 and the step S3, a spray drying mode is adopted to ensure that spherical slurry powder and spherical ceramic feed powder are respectively obtained; in the range of the feeding rate, the size of the feed can be adjusted by adjusting the feeding rate; proper increase of the feed rate can increase the feed particle size; the specific feed rate may be adjusted according to the actual situation.
According to some preferred embodiments, the solvent to rare earth hafnate ceramic block mass ratio is (1-2): 1 (e.g., may be 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1); and/or
In step S3, the binder is used in an amount of 0.5 to 5% (e.g., may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%) of the mass of the rare earth hafnate ceramic block. In the dosage range of the binder, the size of the feed can be adjusted by adjusting the dosage of the binder; the feeding grain diameter can be increased by properly increasing the consumption of the binder; the specific dosage of the binder can be adjusted according to actual conditions.
The invention provides in a third aspect the use of the nanostructured rare earth hafnate ceramic powder feed for thermal spraying according to the first aspect in the field of thermal/environmental barrier coatings.
The rare earth hafnate ceramic powder with the nano structure provided by the invention has the advantages of high feeding sphericity, uniform particle size distribution, good fluidity, uniform thickness, high compactness, higher fracture toughness and damage tolerance, higher stability at high temperature and excellent comprehensive performance.
In order to more clearly illustrate the technical scheme and advantages of the present invention, the present invention will be further described below with reference to examples.
The materials and the reagents in the invention can be obtained by direct purchase or self-synthesis in the market, and the specific model is not limited; it can be understood that spherical ceramic powder with single particle size cannot be obtained by spray drying, so that the rare earth hafnate ceramic powder feed in the embodiment of the invention is formed by mixing feeds with particle size distribution within a certain range.
The fluidity test method of the rare earth hafnate ceramic powder feed provided by the embodiment of the invention comprises the following steps:
the fluidity of the feed was tested using a HYL-102 Hall flow rate meter: 50g of the feed was placed in a standard funnel with a 5mm aperture, the time required for the feed to completely flow out of the aperture was recorded with a stopwatch, and the time required for the feed to completely flow out was divided by the mass of the feed to give fluidity.
Flow state: the fluidity of the feed can be judged by calculating the ratio of the tap density to the apparent density, i.e. the Hausner ratio; when the Hausner ratio is greater than 1.4, the feed is in non-flowability and cohesiveness; when the Hausner ratio is between 1 and 1.25, the feed is in a free-flowing state.
Example 1
(1) 100mL of deionized water, 500g of grinding balls, 100g of ytterbium oxide with the average particle size of 30nm and hafnium oxide with the average particle size of 40nm are put into a ball milling tank, uniformly stirred for 24 hours, added with a polyvinyl alcohol (PVA) binder and continuously stirred for 2 hours to obtain slurry; wherein the mol ratio of ytterbium oxide to hafnium oxide is 2:3, and the dosage of the polyvinyl alcohol binder is 0.2% of the total mass of ytterbium oxide and hafnium oxide;
(2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, firstly preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and then sintering for 3 hours at 1500 ℃ to obtain a ytterbium hafnate ceramic block with a nano structure;
(3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 20mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 2 percent of the mass of the ytterbium hafnate ceramic block;
(4) And (3) cracking and removing glue from the spherical ceramic powder to remove the binder in the spherical ceramic powder, wherein the cracking temperature is 550 ℃, and the cracking time is 2 hours, so as to obtain the ytterbium hafnate ceramic powder feed with the particle size distribution of 10-40 mu m and the nanostructure.
As can be seen from FIG. 1, the ytterbium hafnate powder prepared in example 1 has high feed sphericity, which is beneficial to the powder flowing during spraying; as can be seen from FIG. 2, the ytterbium hafnate powder feed ball prepared in example 1 has a compact inner part and a solid structure, and the prepared coating has low porosity and high bonding strength; as can be seen from FIG. 3, ytterbium hafnate powder prepared in example 1 has relatively uniform particle size distribution and reasonable distribution, has particle size distribution of 10-40 μm, and is easy to prepare a coating under relatively low power; as can be seen from fig. 4 to 6, the ytterbium hafnate powder feed prepared in example 1 is a single phase, the ytterbium hafnate powder feed is composed of nanocrystals, and the size of the crystal grains of the nanocrystals is 1-50 nm; as can be seen from fig. 7, the rare earth oxide and hafnium oxide completely reacted.
The fluidity test result of the ytterbium hafnate powder feed prepared in example 1 was 31.4s/50g; the ratio of tap density to bulk density (Hausner) was measured to be 1.22, indicating that the feed was in a free-flowing state.
Example 2
(1) 100mL of deionized water, 500g of grinding balls, 100g of mixture of gadolinium oxide with the average particle size of 30nm and hafnium oxide with the average particle size of 40nm are put into a ball milling tank, uniformly stirred for 24 hours, added with a polyvinyl alcohol (PVA) binder and continuously stirred for 2 hours to obtain slurry; wherein the mol ratio of gadolinium oxide to hafnium oxide is 2:3, and the dosage of the polyvinyl alcohol binder is 0.2% of the total mass of gadolinium oxide and hafnium oxide;
(2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, firstly preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and then sintering for 3 hours at 1500 ℃ to obtain a gadolinium hafnate ceramic block with a nano structure;
(3) Adding 100mL of deionized water, 500g of grinding balls and 100g of gadolinium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 20mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 2% of the mass of the gadolinium hafnate ceramic block;
(4) And (3) cracking and removing glue from the spherical ceramic powder to remove the binder in the spherical ceramic powder, wherein the cracking temperature is 550 ℃, and the cracking time is 2 hours, so as to obtain the gadolinium hafnate ceramic powder feed with the particle size distribution of 10-40 mu m and the nano structure.
Example 3
Example 3 is substantially the same as example 1 except that: ytterbium oxide is replaced by scandium oxide; the scandium hafnate ceramic powder feed with the grain size distribution of 10-40 mu m and the nano structure is prepared.
Example 4
Example 4 is substantially the same as example 1 except that: ytterbium oxide is replaced by yttrium oxide; the yttrium hafnate ceramic powder feed with the grain size distribution of 10-40 mu m and the nano structure is prepared.
Example 5
Example 5 is substantially the same as example 1 except that: ytterbium oxide is replaced by holmium oxide respectively; the holmium hafnate ceramic powder feed with the particle size distribution of 10-40 mu m and the nano structure is prepared.
Example 6
Example 6 is substantially the same as example 1 except that: ytterbium oxide is replaced by erbium oxide; the erbium hafnate ceramic powder feed with the grain size distribution of 10-40 mu m and the nano structure is prepared.
Example 7
Example 7 is substantially the same as example 1 except that: replacing ytterbium oxide with lutetium oxide; the lutetium hafnate ceramic powder feed with the grain size distribution of 10-40 mu m and the nano structure is prepared.
Example 8
(1) 100mL of deionized water, 500g of grinding balls, 100g of ytterbium oxide with the average particle size of 30nm and hafnium oxide with the average particle size of 40nm are put into a ball milling tank, uniformly stirred for 24 hours, added with a polyvinyl alcohol (PVA) binder and continuously stirred for 2 hours to obtain slurry; wherein the mol ratio of ytterbium oxide to hafnium oxide is 2:3, and the dosage of the polyvinyl alcohol binder is 0.2% of the total mass of ytterbium oxide and hafnium oxide;
(2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, firstly preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and then sintering for 3 hours at 1500 ℃ to obtain a ytterbium hafnate ceramic block with a nano structure;
(3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 50mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 2 percent of the mass of the ytterbium hafnate ceramic block;
(4) And (3) cracking and removing glue from the spherical ceramic powder to remove the binder in the spherical ceramic powder, wherein the cracking temperature is 550 ℃, and the cracking time is 2 hours, so as to obtain the ytterbium hafnate ceramic powder feed with the nano structure and the particle size distribution of 10-40 mu m.
Example 9
(1) 100mL of deionized water, 500g of grinding balls, 100g of ytterbium oxide with the average particle size of 30nm and hafnium oxide with the average particle size of 40nm are put into a ball milling tank, uniformly stirred for 24 hours, added with a polyvinyl alcohol (PVA) binder and continuously stirred for 2 hours to obtain slurry; wherein the mol ratio of ytterbium oxide to hafnium oxide is 2:3, and the dosage of the polyvinyl alcohol binder is 0.2% of the total mass of ytterbium oxide and hafnium oxide;
(2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, firstly preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and then sintering for 4 hours at 1550 ℃ to obtain a ytterbium hafnate ceramic block with a nano structure;
(3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 50mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 2 percent of the mass of the ytterbium hafnate ceramic block;
(4) And (3) cracking and removing glue from the spherical ceramic powder to remove the binder in the spherical ceramic powder, wherein the cracking temperature is 550 ℃, and the cracking time is 2 hours, so as to obtain the ytterbium hafnate ceramic powder feed with the particle size distribution of 10-40 mu m and the nanostructure.
Example 10
(1) 100mL of deionized water, 500g of grinding balls, 100g of ytterbium oxide with the average particle size of 30nm and hafnium oxide with the average particle size of 40nm are put into a ball milling tank, uniformly stirred for 24 hours, added with a polyvinyl alcohol (PVA) binder and continuously stirred for 2 hours to obtain slurry; wherein the mol ratio of ytterbium oxide to hafnium oxide is 2:3, and the dosage of the polyvinyl alcohol binder is 0.2% of the total mass of ytterbium oxide and hafnium oxide;
(2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, firstly preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and then sintering for 4 hours at 1550 ℃ to obtain a ytterbium hafnate ceramic block with a nano structure;
(3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 50mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 5% of the mass of ytterbium hafnate ceramic block;
(4) And (3) cracking and removing glue from the spherical ceramic powder to remove the binder in the spherical ceramic powder, wherein the cracking temperature is 550 ℃, and the cracking time is 2 hours, so that the rare earth hafnate ceramic powder feed with the nano structure and the particle size distribution of 10-40 mu m is obtained.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: (2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and then sintering for 3 hours at 1200 ℃ to obtain the ytterbium hafnate ceramic block.
Comparative example 1 cannot obtain ytterbium hafnate ceramic block because the sintering temperature is too low.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that: (2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and sintering for 3 hours at 1800 ℃ to obtain the ytterbium hafnate ceramic block.
Comparative example 2 the size of the grains in the ytterbium hafnate ceramic block was too large due to the too high sintering temperature.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: (2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and sintering for 1 hour at 1500 ℃ to obtain the ytterbium hafnate ceramic block.
Comparative example 3 the ytterbium oxide and hafnium oxide did not react completely due to the short sintering time, and the ytterbium hafnate ceramic block could not be obtained with high purity.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: (2) Spray drying the slurry by adopting a spray drying technology to obtain spherical slurry powder, wherein the feeding rate of spray drying is 20mL/min, the inlet temperature is 220 ℃, and the outlet temperature is 100 ℃; then placing the spherical slurry powder into a zirconia crucible, preserving heat for 2 hours at 600 ℃ at a heating rate of 5 ℃/min, and sintering for 6 hours at 1500 ℃ to obtain the ytterbium hafnate ceramic block.
Comparative example 4 the grain size was greater than nano-scale due to the continuous growth of grains in ytterbium hafnate ceramic blocks due to the excessive sintering time.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that: (3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 20mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 0.2 percent of the mass of the rare earth hafnate ceramic powder.
As shown in FIG. 12, in comparative example 5, the spherical ytterbium hafnate ceramic powder feed was not obtained due to the too small amount of binder.
Comparative example 6
Comparative example 6 is substantially the same as example 1 except that: (3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 20mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 8 percent of the quality of the rare earth hafnate ceramic powder.
In comparative example 6, the binder is excessively used to cause excessive viscosity of the slurry, so that the nozzle of the granulator is easily blocked, the performance of the granulated powder is adversely affected, the loose packing density is increased along with the increase of the content of the binder, and meanwhile, the binder is excessively high, and foreign phases remain in the process of discharging the binder, so that the binder is not beneficial to discharging the binder.
Comparative example 7
Comparative example 7 is substantially the same as example 1 except that: (3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 10mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 2 percent of the mass of the ytterbium hafnate ceramic block.
In the comparative example 7, due to the fact that the feeding speed is too small, mist drop particles are small, moisture evaporation is too fast, and finally obtained spherical ytterbium hafnate ceramic powder feeding particles are small, low in sphericity and poor in fluidity, and cannot be used for normal thermal spraying.
Comparative example 8
Comparative example 8 is substantially the same as example 1 except that: (3) Adding 100mL of deionized water, 500g of grinding balls and 100g of ytterbium hafnate ceramic blocks into a ball milling tank, uniformly stirring for 8h, adding a binder, continuously stirring for 2h, performing spray drying, wherein the feeding rate of the spray drying is 80mL/min, and the inlet temperature is 230 ℃ and the outlet temperature is 110 ℃ to obtain spherical ceramic powder; wherein, the dosage of the polyvinyl alcohol binder is 2 percent of the mass of the ytterbium hafnate ceramic block.
Comparative example 8 is too high in feed rate, so that on one hand, the nozzle of the granulator is easily blocked, on the other hand, the prepared powder particles are larger, the powder particles cannot be fully melted in the coating preparation process, the porosity of the formed coating is too high, the coating is easily fallen off due to scouring, and the normal protective effect on the matrix cannot be achieved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The nano-structure rare earth hafnate ceramic powder feed for thermal spraying is characterized by comprising nano crystals; the grain size of the rare earth hafnate ceramic powder feed is 10-40 mu m; the grain size of the nanocrystalline is 1-50 nm;
the preparation method of the rare earth hafnate ceramic powder feed comprises the following steps:
s1, performing ball milling and mixing on rare earth oxide, hafnium oxide, a solvent and a binder to obtain slurry; the rare earth oxide is one of scandium oxide, yttrium oxide, ytterbium oxide, gadolinium oxide, holmium oxide, erbium oxide and lutetium oxide;
s2, drying, loose sintering the slurry to obtain a rare earth hafnate ceramic block; the loose sintering is carried out by preserving heat for 1-2 hours at 500-750 ℃ at a heating rate of 5-10 ℃/min, and then sintering for 2-4 hours at 1450-1600 ℃;
s3, ball-milling, mixing and drying the rare earth hafnate ceramic block, the solvent and the binder to obtain spherical ceramic powder; the drying is spray drying, and the feeding rate of the spray drying is 20-60 mL/min;
s4, cracking and discharging glue from the spherical ceramic powder to obtain the rare earth hafnate ceramic powder feed; the cracking and glue discharging are carried out for 1-3 hours at the temperature of 500-750 ℃;
in the step S3, the using amount of the binder is 0.5-5% of the mass of the rare earth hafnate ceramic block.
2. The rare earth hafnate ceramic powder feed of claim 1, wherein in step S1 the molar ratio of rare earth oxide to hafnium oxide is 2:3.
3. The rare earth hafnate ceramic powder feed according to claim 1, wherein in step S1, the solvent is used in an amount of (1/2 to 2/3) of the mass of the slurry; and/or
The mass of the binder is 0.2-0.5% of the total mass of the rare earth oxide and the hafnium oxide.
4. The rare earth hafnate ceramic powder feed according to claim 2 or 3, characterized in that in step S1, the particle size of the rare earth oxide is 15 to 40nm; and/or
The grain size of the hafnium oxide is 30-50 nm.
5. The rare earth hafnate ceramic powder feed of claim 1, wherein in step S1 and step S3, the solvent is one of deionized water and ethanol; the binder is polyvinyl alcohol; and/or
In the step S2 and the step S3, the inlet temperature is 190-230 ℃, and the outlet temperature is 90-110 ℃.
6. The rare earth hafnate ceramic powder feed according to claim 1, wherein in step S3, the mass ratio of the solvent to the rare earth hafnate ceramic block is (1-2): 1.
7. Use of a rare earth hafnate ceramic powder feed according to any one of claims 1 to 6 in the field of thermal/environmental barrier coatings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310055882.0A CN116023136B (en) | 2023-01-19 | 2023-01-19 | Nano-structure rare earth hafnate ceramic powder feed for thermal spraying and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310055882.0A CN116023136B (en) | 2023-01-19 | 2023-01-19 | Nano-structure rare earth hafnate ceramic powder feed for thermal spraying and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116023136A CN116023136A (en) | 2023-04-28 |
| CN116023136B true CN116023136B (en) | 2024-02-09 |
Family
ID=86070422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310055882.0A Active CN116023136B (en) | 2023-01-19 | 2023-01-19 | Nano-structure rare earth hafnate ceramic powder feed for thermal spraying and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116023136B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747428A (en) * | 2017-01-16 | 2017-05-31 | 西北工业大学 | The preparation method of one-step synthesis method various grain sizes hafnium acid yttrium ceramic powder |
| CN107129295A (en) * | 2017-03-10 | 2017-09-05 | 上海航天设备制造总厂 | Ceramic feeding powder for preparing automatically cleaning hot-spraying coating and preparation method thereof |
| CN109355613A (en) * | 2018-12-14 | 2019-02-19 | 武汉理工大学 | A kind of high temperature high emissivity hafnium oxide base infrared radiating coating and preparation method thereof |
| CN110204331A (en) * | 2019-05-27 | 2019-09-06 | 全南晶鑫环保材料有限公司 | A kind of preparation method of yttrium stabilized hafnia spherical powder used for hot spraying |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7449128B2 (en) * | 2004-06-21 | 2008-11-11 | General Electric Company | Scintillator nanoparticles and method of making |
-
2023
- 2023-01-19 CN CN202310055882.0A patent/CN116023136B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747428A (en) * | 2017-01-16 | 2017-05-31 | 西北工业大学 | The preparation method of one-step synthesis method various grain sizes hafnium acid yttrium ceramic powder |
| CN107129295A (en) * | 2017-03-10 | 2017-09-05 | 上海航天设备制造总厂 | Ceramic feeding powder for preparing automatically cleaning hot-spraying coating and preparation method thereof |
| CN109355613A (en) * | 2018-12-14 | 2019-02-19 | 武汉理工大学 | A kind of high temperature high emissivity hafnium oxide base infrared radiating coating and preparation method thereof |
| CN110204331A (en) * | 2019-05-27 | 2019-09-06 | 全南晶鑫环保材料有限公司 | A kind of preparation method of yttrium stabilized hafnia spherical powder used for hot spraying |
Non-Patent Citations (1)
| Title |
|---|
| 《几种稀土铪酸盐的制备与性能研究》;胡万鹏;中国博士学位论文全文数据库(第08期);第20页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116023136A (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101182207B (en) | Spraying powder containing yttrium oxide and preparation method thereof | |
| US7838462B2 (en) | Ceramic support capable of supporting catalyst, catalyst-ceramic body and processes for producing same | |
| EP2474590B1 (en) | Phosphor particles and making method | |
| CN1139949A (en) | Alpha alumina-based abrasive grain having an as sintered outer surface | |
| CN105384190B (en) | Method for preparing nano samarium zirconate powder used for additive manufacturing and feeding | |
| WO2003004437A1 (en) | Translucent rare earth oxide sintered article and method for production thereof | |
| CN102453955B (en) | Crucible coating for purification and ingot casting of solar grade polysilicon and preparation method thereof as well as crucible | |
| CN1865190A (en) | Zirconia/silicon carbide composite nano powder for hot spraying and its production method | |
| CN107285747B (en) | Production process of corundum-zirconia abrasive | |
| CN101066883A (en) | Freeze forming prepn process of ternary lithium ceramic microphere | |
| CN110002870A (en) | A kind of rare earth tantalate ceramics and preparation method thereof of anti-low melting point oxide corrosion | |
| EP1055743B1 (en) | Vapor deposition material | |
| CN201857440U (en) | Crucible for purification and ingot casting of solar-grade polysilicon | |
| CN110041071A (en) | Three rare earth niobates ceramics of one kind and preparation method thereof | |
| CN112662982A (en) | Nano-structure Yb suitable for plasma spraying2Si2O7Preparation method of spherical feed | |
| CN1202043C (en) | Prepn of large grain spherical submicron/nano composite fiber-ceramic powder | |
| CN109942294A (en) | A kind of rare earth samarium tantalate ceramics of different stoichiometric ratios and preparation method thereof of anti-low melting point oxide corrosion | |
| CN102503538A (en) | Continuously pore-forming silicon carbide ceramic material and preparation method for same | |
| CN116023136B (en) | Nano-structure rare earth hafnate ceramic powder feed for thermal spraying and preparation method and application thereof | |
| JP4743387B2 (en) | Method for producing aluminum nitride powder | |
| KR20190065974A (en) | COMPOSITE MATERIAL COMPRISING AT LEAST ONE FIRST MATERIAL AND PARTICLES WITH A NEGATIVE COEFFICIENT α OF THERMAL EXPANSION, AND ADHESIVE BONDING MATERIAL COMPRISING THE COMPOSITE MATERIAL | |
| CN105272315B (en) | A kind of porous zirconium calcium aluminate and preparation method thereof | |
| CN115322000B (en) | Magnesium-calcium tundish dry material and preparation method thereof | |
| CN106810283B (en) | Mullite-chromium lightweight castable | |
| CN105503208B (en) | A kind of method that metering nozzle is prepared using plural gel stabilizing zirconia as matrix |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |