CN103225062B - ZrO2 thermal barrier coating prepared by electron-beam physical vapor desorption - Google Patents

ZrO2 thermal barrier coating prepared by electron-beam physical vapor desorption Download PDF

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CN103225062B
CN103225062B CN201310181530.6A CN201310181530A CN103225062B CN 103225062 B CN103225062 B CN 103225062B CN 201310181530 A CN201310181530 A CN 201310181530A CN 103225062 B CN103225062 B CN 103225062B
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zro
barrier coating
thermal barrier
powder
target
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CN103225062A (en
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徐小峰
郑月宗
鲁海军
李雪冰
夏宏生
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STATE GRID ZHEJIANG LONGYOU COUNTY POWER SUPPLY CO., LTD.
State Grid Zhejiang Yuyao Power Supply Company
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STATE GRID ZHEJIANG YUYAO POWER SUPPLY Co
STATE GRID ZHEJIANG LONGYOU COUNTY POWER SUPPLY Co Ltd
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Abstract

The invention relates to a ZrO2 thermal barrier coating prepared by electron-beam physical vapor desorption. A preparation method of the ZrO2 thermal barrier coating comprises the following steps of: firstly, preparing stable nanometer zirconia powder with a large specific surface area by adopting ZrO(NO3)2 as a zirconium source and dropwise adding epoxypropane, and then preparing the ZrO2 thermal barrier coating by adding a right amount of Lu2O3, In2O3, A12O3 and TiO2 on the basis of the prepared stable nanometer zirconia powder with the large specific surface area. The prepared coating has good stability and high corrosion-resistant performance.

Description

The ZrO that a kind of electro beam physics vapour deposition legal system is standby 2thermal barrier coating
Technical field
The invention belongs to materials science field, be specifically related to a kind of ZrO standby by electro beam physics vapour deposition legal system 2thermal barrier coating.
Background technology
Thermal barrier coating (Thermal Barrier Coating) is one deck ceramic coating, it is deposited on the surface of refractory metal or superalloy, thermal barrier coating plays heat-blocking action for base material, reduce base reservoir temperature, the device (as engine turbine blade) made with it at high temperature can be run, and device (engine etc.) thermo-efficiency can be improved reach more than 60%.
U.S. NASA (National Aeronautics and Space Administration)-Lewis research centre, in order to improve gas-turbine blade, the high temperature resistance of rocket engine and corrosion resistance nature, just proposes thermal barrier coating concept as far back as twentieth century the fifties.After the Material selec-tion and preparation technology of coating carry out the exploration of long period, the beginning of the eighties achieves important breakthrough, and solid foundation has been established in the application for thermal barrier coating.Document shows, current advanced thermal barrier coating can reduce high-temperature engine hot-end component about temperature 170K under Working environment.Along with the application of thermal barrier coating on high-temperature engine hot-end component, people recognize that the application of thermal barrier coating not only can reach and improve matrix resistance to high temperature corrosion ability, the object of further raising engine operating temperature, and fuel oil consumption can be reduced, raise the efficiency, extend the work-ing life of hot-end component.Compared with development of new high temperature alloy, the research cost of thermal barrier coating is relatively low, and technique is practicable also.
Along with the development of Aeronautics and Astronautics and civilian technology, the use temperature of hot-end component requires more and more higher, with the extreme condition of reach a high temperature alloy and monocrystal material.For the heating part of gas turbine as nozzle, blade, combustion chamber, they are in the severe environment such as high temperature oxidation and high temperature gas flow erosion, and withstand temp, up to 1100 DEG C, has exceeded the ultimate temperature (1075 DEG C) that high temperature nickel alloy uses.The high strength of metal, high tenacity are combined a little prepared thermal barrier coating can solve the problem with the resistant to elevated temperatures of pottery, it can play heat insulation, anti-oxidant, etch-proof effect, on the hot junction materials such as steam turbine, oil electric engine, jet engine, obtain certain application, and improve the work-ing life of hot-end component.
Zirconium dioxide is the main raw material in current thermal barrier coating, zirconium dioxide (chemical formula: ZrO 2, or claim zirconium white) and be the main oxides of zirconium, be white odorless, tasteless crystal under usual condition, be insoluble in water, hydrochloric acid and dilute sulphuric acid.Generally normal containing a small amount of hafnium oxide.Chemical property torpescence, but high-melting-point, the character of high resistivity, high refractive index and low thermal coefficient of expansion, makes it become important high temperature material, ceramic insulating material and ceramic opalizer.
Pure zirconium dioxide is a kind of senior refractory raw material, and its melt temperature is about 2900 DEG C.It can improve the high temperature viscosity of glaze and expand the temperature range of viscosity B coefficent, has good thermostability, when its content is 2%-3%, can improve the freedom from cracking performance of glaze.Unreactiveness also because of it is large, therefore can improve chemical stability and the acid and alkali-resistance ability of glaze, can also play the effect of opacifying agent. and in architectural pottery glaze, use zircon, general consumption is 8%-12% more.And be the main raw material of " under glaze white ", zirconium white is the good assistant toner of yellow-green pigment, obtains the zirconium white that good vanadium zirconium yellow pigment must select matter pure if want.
The chemical property of zirconium dioxide is very stable, the zirconium dioxide character especially torpescence after calcining.It can by Thickish hot hydrochloric acid, sulfuric acid, hydrofluoric acid and nitric acid corrode, can generate zirconate with oxyhydroxide, oxide compound and carbonate congruent melting under high temperature, be in fact high molecular mixed metal oxide.Zirconium dioxide and carbon and chlorine pyroreaction, or and carbon tetrachloride reaction, generate zirconium tetrachloride and zirconyl chloride, hydrolysis is got back zirconium dioxide.It generates zirconium carbide with carbon effect in electric arc.
The preparation method of zirconium dioxide is more, and the sol-gel method wherein in wet chemistry method is due to the trickle and narrowly distributing of material particle size of preparation; The material purity obtained is high, chemical composition is even; The advantages such as lower than traditional method 400 DEG C-500 DEG C of firing temperature are ideal and have the method preparing zirconium dioxide powder of practical value at present.
From french chemist J.J.Ebelmen SiCl in 1846 4after mixing with ethanol, find to occur be hydrolyzed and define gel in wet air.Colloidal sol in 100 years-gel technique gradual perfection also obtains tremendous development.After 1970, sol-gel technique (Sol-Gel method) is as the emerging manufacturing technology of a kind of high-tech, obtain the great attention of scientific and technological circle and business circles, the composite oxide material being difficult to obtain in glass, ultrafine powder, oxide coating, fiber, function ceramics powder and traditional method is succeeded application.
Sol-gel process is one of wet-chemical reaction method, usually presoma is made with metal alkoxide or inorganic salt, by these raw material Homogeneous phase mixing under liquid phase, and be hydrolyzed, condensation chemical reaction, form stable vitreosol system in the solution, colloidal sol is slowly polymerized through between ageing micelle, forms the gel of three-dimensional space network structure, be filled with the solvent lost flowability between gel network, form gel.Gel prepares the material of molecule and even nanometer substructure through super-dry, sintering curing.
Solvation:
M(H 2O)nz+=M(H 2O)n-1(OH)(z-1)+H +
Hydrolysis reaction:
M(OR)n+xH 2O=M(OH)x(OR)n-x+xROH------M(OH)n
Polycondensation:
Dehydration polycondensation :-M-OH+HO-M-=-M-O-M-+H 2o
Lose alcohol polycondensation :-M-OR+HO-M-=-M-O-M-+ROH
Inorganic salt or metal alkoxide are made presoma, by these raw material Homogeneous phase mixing under liquid phase, and be hydrolyzed, condensation chemical reaction, or solidifying form colloidal sol by separating, the principal element affecting this process has the temperature of reaction of water, add-on, rate of addition, pH etc.The raising of temperature contributes to the hydrolysis of alkoxide, to the alkoxide (as silicon alkoxide) low to hydrolytic activity, its hydrolysis often need be carried out under heating state, that water speed increases the increase of micelle molecular kinetic energy, probability of collision also increases, rate of polymerization is fast, thus cause aerosol time to shorten, on the other hand, under comparatively high temps, the volatilization of solvent alcohol is also accelerated, be equivalent to add reactant concn, also colloidal sol speed simultaneous temperature is accelerated to a certain extent also unsuitable too high, too high temperature can make the colloidal sol of generation relatively unstable, and easily have the hydrolytic-polymeric reaction of multi-products, generate not volatile organic matter.Therefore, when guaranteeing to generate colloidal sol, lesser temps is taked as far as possible.The add-on of water should add according to stoichiometric ratio.The plastic mass that stoichiometric ratio adds is good, and the time of plastic is relatively short.If amount of water extends aerosol time lower than the consumption required for stoichiometric ratio can make alcoholization hydrolysis reaction slow; If amount of water, higher than in the consumption required for stoichiometric ratio, can make solution become dilution, soltion viscosity declines, and plastic is more difficult.When dripping alkoxide solution, rate of addition should be observed when other are consistent, drop rate is faster, gelation rate is also fast, but rate of addition is too fast, local can be made to be hydrolyzed too fast generation polymerization and gel and generate precipitation, a part of sol solutions is hydrolyzed and finally cannot obtains homogeneous gel simultaneously, so also should uniform stirring be aided with when reacting, thus ensure to obtain the gel be evenly distributed.The pH of reaction solution is different, and its reaction mechanism is different, thus to the hydrolytie polycondensation of same metal alkoxide, often produces structure, polycondensation that form is different.Research shows, when pH is less, polycondensation speed is far longer than hydrolysis reaction, is hydrolyzed by H +close motor reason cause, polycondensation starts before complete hydrolysis, and therefore polycondensate degree of crosslinking is low; When pH is larger, the hydrolysis reaction system of system is by [OH -] nucleophilic substitution cause, hydrolysis rate is greater than nucleophilic speed, forms high polymer, has higher degree of crosslinking, can select suitable acid base catalysator by the material requirements that specifically will produce.
Form stable vitreosol system in the solution, colloidal sol is slowly polymerized through between ageing micelle, and form the gel of three-dimensional space network structure, the colloidal sol of tool mobility forms the gelling system that can not flow after polycondensation.Through polycondensation formed sol solution in ageing time, the further agglomeration of polymkeric substance becomes granule submanifold, and they mutually collide and connect into macroparticle bunch, and meanwhile, liquid phase is wrapped in solid skeleton and loses flowing, formed gel.Be filled with the solvent lost flowability between gel network, form gel.Gel prepares the material of molecule and even nanostructure through super-dry, sintering curing and subsequent heat treatment.It is that preparation nano material is comparatively commonly used and novel method that is convenient and easy, that do not need severe condition.
But in prior art, the usual metal alkoxide adopted is as the organic procedures of presoma, although preparing product has the ultra-fine ZrO of bigger serface 2powder, but the method cost is higher, and zirconium alkoxide is expensive, not easily realizes suitability for industrialized production.Prior art also has to be avoided using expensive alkoxide, and the oxalic acid adopting decomposition can not produce obnoxious flavour is precipitation agent, has also prepared ZrO 2nano-powder.The sol-gel method of this modification adds the different tensio-active agent of molecular size range before coagulation, adopt dehydrated alcohol ultrasonic disperse after coagulation, effectively can eliminate agglomeration, however numerous and diverse according to the method preparation process, and amount of surfactant is difficult to control, production cost is higher.At present still not about employing ZrO (NO 3) 2as zirconium source and drip propylene oxide method prepare large-specific-area stable nano zirconium oxide powder research report.
In addition, people are confirmed by a large amount of tests, and the main medium gas turbine engine scribbling thermal barrier coating being produced to thermal etching effect is NaCl, Na 2sO 4, V 2o 5deng.At different conditions, they are attached to the surface of high-temperature component with gaseous state, liquid state or solid-state form.Wherein NaCl is mainly from the pollution of air or seawater, especially at sea or the aircraft of operation in coastal atmospheric environment.Na 2sO 4and V 2o 5not directly from air.Na 2sO 4combustion oxidation mainly from sulphur in rocket engine fuel and compound thereof reacts.In the technique preparing thermal barrier coating, usually with Y in prior art 2o 3, Ta 2o 5, Nd 2o 3or or La 2o 3as stabilizer element, the thermal etching that the impurity chemical reaction at high temperature such as vanadic salts, sodium salt in mentioned component and oil plant causes also is the common factors causing coating failure.Corrode fused salt under high temperature and penetrate into coating by the hole in plasma spraying coating, normal and Na 2sO 4-V 2o 5fused salt reacts, and causes fused salt to infiltrate along thermal barrier coating, and reacting with tack coat makes thermal barrier coating unsticking lose efficacy.
Summary of the invention
The object of this invention is to provide a kind of ZrO standby by electro beam physics vapour deposition legal system 2thermal barrier coating, first passes through about employing ZrO (NO 3) 2drip propylene oxide method prepare large-specific-area stable nano zirconium oxide powder as zirconium source, then on the basis of prepared large-specific-area stable nano zirconium oxide powder, add appropriate Lu 2o 3, In 2o 3, Al 2o 3and TiO 2prepare ZrO 2thermal barrier coating, obtained coating stability is good and have higher corrosion resistance.
Goal of the invention of the present invention is achieved through the following technical solutions: a kind of ZrO standby by electro beam physics vapour deposition legal system 2thermal barrier coating, is characterized in that, this ZrO 2thermal barrier coating comprises following raw material:
The bigger serface stabilized nanoscale ZrO of 30 ~ 35g 2powder,
The stablizer of 4 ~ 6g;
Wherein, described stablizer is Lu 2o 3, In 2o 3, Al 2o 3and TiO 2mixture, Lu in mixture 2o 3, In 2o 3, Al 2o 3and TiO 2mol ratio be 1:1:1:1
Wherein, described bigger serface stabilized nanoscale ZrO 2powder is prepared by following raw material and step:
(1) ZrO (NO is chosen 3) 2as the zirconates raw material preparing Zirconium powder, choose Y (NO 3) 36H 2o, as stablizer raw material, takes the ZrO (NO of 55 ~ 60g 3) 2with the Y (NO of 10 ~ 12g 3) 36H 2o, fully mixes;
(2) ZrO (NO step 1) mixed 3) 2with Y (NO 3) 36H 2o mixture joins in the deionized water of 450 ~ 500 ml, is uniformly mixed, filters, then adds 190 ~ 200ml ethanol, continues to be uniformly mixed;
(3) in step 2) add 7 ~ 9ml methane amide again in obtained solution, stir 25 ~ 35min;
(4) then in the solution of step 3), add 165 ~ 170ml 1,2 epoxy prapane again, dropping limit, limit is stirred;
(5) pour in culture dish, with preservative film sealing, be placed in pallet, the baking oven putting into 60 DEG C carries out gelation and ageing process, obtains wet gel;
(6) gel seal room temperature is placed 24 h, smash to pieces, be positioned in 110 DEG C of thermostatic drying chambers and dry;
(7) xerogel is moved into crucible, thermal treatment in 600 DEG C of retort furnaces, obtains presoma;
(8) again by presoma respectively 700 DEG C, 800 DEG C, 1000 DEG C and 1200 DEG C of thermal treatments, obtain the ZrO of nano level bigger serface 2powder;
And,
Above-mentioned thermal barrier coating is prepared by following steps:
By the bigger serface stabilized nanoscale ZrO of 30 ~ 35g 2the stablizer mixing and ball milling of powder and 4 ~ 6g, the speed of ball milling is 270 ~ 290r/min, and the time of described ball milling is 2h;
Obtained mixing material is made base substrate through isostatic cool pressing, is then sinter 3 ~ 4h in the retort furnace of 1500 ~ 1600 DEG C to make polynary stabilizing zirconia target in temperature;
Target is put into electro beam physics vapour deposition equipment crucible again, with high-power electron beam, target is melted, target evaporates, and the target atom of evaporation to deposit to above target through pretreated substrate surface, forms the anti-fused salt corrosion thermal barrier coating of polynary stabilizing zirconia.
Namely ZrO of the present invention is prepared 2the entire protocol of thermal barrier coating is:
A, nano level ZrO 2the preparation of powder
(1) ZrO (NO is chosen 3) 2as the zirconates raw material preparing Zirconium powder, choose Y (NO 3) 36H 2o, as stablizer raw material, takes the ZrO (NO of 55 ~ 60g 3) 2with the Y (NO of 10 ~ 12g 3) 36H 2o, fully mixes;
(2) ZrO (NO step 1) mixed 3) 2with Y (NO 3) 36H 2o mixture joins in the deionized water of 450 ~ 500 ml, is uniformly mixed, filters, then adds 190 ~ 200ml ethanol, continues to be uniformly mixed;
(3) in step 2) add 7 ~ 9ml methane amide again in obtained solution, stir 25 ~ 35min;
(4) then in the solution of step 3), add 165 ~ 170ml 1,2 epoxy prapane again, dropping limit, limit is stirred;
(5) pour in culture dish, with preservative film sealing, be placed in pallet, the baking oven putting into 60 DEG C carries out gelation and ageing process, obtains wet gel;
(6) gel seal room temperature is placed 24 h, smash to pieces, be positioned in 110 DEG C of thermostatic drying chambers and dry;
(7) xerogel is moved into crucible, thermal treatment in 600 DEG C of retort furnaces, obtains presoma;
(8) again by presoma respectively 700 DEG C, 800 DEG C, 1000 DEG C and 1200 DEG C of thermal treatments, obtain the ZrO of nano level bigger serface 2powder;
B, prepare thermal barrier coating
(9) choose by step 1)-8) ZrO of 30 ~ 35g for preparing 2powder, then the stablizer choosing 4 ~ 6g, described stablizer is Lu 2o 3, In 2o 3, Al 2o 3and TiO 2mixture, Lu in mixture 2o 3, In 2o 3, Al 2o 3and TiO 2mol ratio be 1:1:1:1;
(10) by the ZrO of step 9) 2powder and stablizer mixing and ball milling, the speed of ball milling is 270 ~ 290r/min, and the time of described ball milling is 2h;
(11) mixing material that step 10) is obtained being made base substrate through isostatic cool pressing, is then sinter 3 ~ 4h in the retort furnace of 1500 ~ 1600 DEG C to make polynary stabilizing zirconia target in temperature;
(12) target is put into electro beam physics vapour deposition equipment crucible again, with high-power electron beam, target is melted, target evaporates, and the target atom of evaporation to deposit to above target through pretreated substrate surface, forms the anti-fused salt corrosion thermal barrier coating of polynary stabilizing zirconia.
About technique effect of the present invention.First, at ZrO 2in the preparation of powder, choose ZrO (NO 3) 2as the zirconates raw material preparing Zirconium powder, choose Y (NO 3) 36H 2o is as stablizer raw material, and select the composition of the addition of suitable presoma, digestion time, Ageing solution, and adopt inorganic dropping propylene oxide method, thus preparation large-specific-area stable nano zirconium oxide powder, for the thermal barrier coating of follow-up preparation high stability provides the foundation.Then, when preparing thermal barrier coating, owing to have selected Lu 2o 3, In 2o 3, Al 2o 3and TiO 2mixture as stablizer, heat barrier coat material is made base substrate through isostatic cool pressing and sinters, host (ZrO 2) and stablizer (Lu 2o 3, In 2o 3, Al 2o 3with TiO 2) between spread, formed make Lu 2o 3, In 2o 3with Al 2o 3and TiO 2polynary stabilizing zirconia (Tetragonal and metastable tetragonal zirconia phase) target, then target is put into electro beam physics vapour deposition equipment crucible, target melts by high-power electron beam, and target evaporates, the target atom of evaporation deposits to through pretreated substrate surface above target, forms Lu 2o 3, In 2o 3, Al 2o 3and TiO 2polynary stabilizing zirconia (Tetragonal and metastable tetragonal zirconia phase) anti-fused salt corrosion thermal barrier coating.Due to Lu 5+, In 3+, Al 3+and Ti 4+ionic radius be less than Na 2sO 4-V 2o 5v in fused salt 5+ionic radius, and Lu 5+with In 3+defect combined action add In 2o 3anti-Na 2sO 4-V 2o 5fused salt corrosion performance, therefore stablizer Lu 2o 3, In 2o 3, Al 2o 3and TiO 2all and Na 2sO 4-V 2o 5fused salt is difficult to chemical reaction occurs.So Multi-component stable thermal-corrosion-rezirconia zirconia coat material of the present invention has excellent stability and anti-fused salt corrosion performance.Above-mentioned preparation method is not reported in the prior art.
To sum up, thermal barrier coating preparation process prepared by the present invention is scientific and reasonable, and reaction process is easy to control, and product safety is reliable, and has excellent stability and anti-fused salt corrosion performance, can realize suitability for industrialized production.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
embodiment 1
A, nano level ZrO 2the preparation of powder
(1) with ZrO (NO 3) 2as the zirconates raw material preparing Zirconium powder, with Y (NO 3) 36H 2o, as stablizer raw material, takes the ZrO (NO of 55g 3) 2with the Y (NO of 12g 3) 36H 2o, mixing;
(2) ZrO (NO will mixed 3) 2with Y (NO 3) 36H 2o joins in the deionized water of 450 ml, is uniformly mixed, filters, then adds 190ml ethanol, continues to be uniformly mixed;
(3) in step 2) add 7 ~ 9ml methane amide again in obtained solution, stir 25min;
(4) then in the solution of step 3), add 165ml 1,2 epoxy prapane again, dropping limit, limit is stirred;
(5) pour in culture dish, with preservative film sealing, be placed in pallet, the baking oven putting into 60 DEG C carries out gelation and ageing process, obtains wet gel;
(6) gel seal room temperature is placed 24 h, smash to pieces, be positioned in 110 DEG C of thermostatic drying chambers and dry;
(7) xerogel is moved into crucible, thermal treatment in 600 DEG C of retort furnaces, obtains presoma;
(8) again by presoma respectively 700 DEG C, 800 DEG C, 1000 DEG C and 1200 DEG C of thermal treatments, obtain the ZrO of nano level bigger serface 2powder;
B, prepare thermal barrier coating
(9) choose by step 1)-8) ZrO of 35g for preparing 2powder, then the stablizer choosing 4g, described stablizer is Lu 2o 3, In 2o 3, Al 2o 3and TiO 2mixture, Lu in mixture 2o 3, In 2o 3, Al 2o 3and TiO 2mol ratio be 1:1:1:1;
(10) by the ZrO of step 9) 2powder and stablizer mixing and ball milling, the speed of ball milling is 270r/min, and the time of described ball milling is 2h;
(11) mixing material that step 10) is obtained being made base substrate through isostatic cool pressing, is then sinter 4h in the retort furnace of 1500 DEG C to make polynary stabilizing zirconia target in temperature;
(12) again target is put into L2 type electro beam physics vapour deposition equipment crucible, target size is Φ 70mm × 100mm, then with the high-power electron beam that power is 60KW, target is melted, target evaporates, the target atom of evaporation to deposit to above target through pretreated substrate surface, forms the anti-fused salt corrosion thermal barrier coating of polynary stabilizing zirconia.
embodiment 2
A, nano level ZrO 2the preparation of powder
(1) with ZrO (NO 3) 2as the zirconates raw material preparing Zirconium powder, with Y (NO 3) 36H 2o, as stablizer raw material, takes the ZrO (NO of 58g 3) 2with the Y (NO of 11g 3) 36H 2o, mixing;
(2) ZrO (NO will mixed 3) 2with Y (NO 3) 36H 2o joins in the deionized water of 480 ml, is uniformly mixed, filters, then adds 195ml ethanol, continues to be uniformly mixed;
(3) in step 2) add 8ml methane amide again in obtained solution, stir 29min;
(4) then in the solution of step 3), add 168ml 1,2 epoxy prapane again, dropping limit, limit is stirred;
(5) pour in culture dish, with preservative film sealing, be placed in pallet, the baking oven putting into 60 DEG C carries out gelation and ageing process, obtains wet gel;
(6) gel seal room temperature is placed 24 h, smash to pieces, be positioned in 110 DEG C of thermostatic drying chambers and dry;
(7) xerogel is moved into crucible, thermal treatment in 600 DEG C of retort furnaces, obtains presoma;
(8) again by presoma respectively 700 DEG C, 800 DEG C, 1000 DEG C and 1200 DEG C of thermal treatments, obtain the ZrO of nano level bigger serface 2powder;
B, prepare thermal barrier coating
(9) choose by step 1)-8) ZrO of 32g for preparing 2powder, then the stablizer choosing 5g, described stablizer is Lu 2o 3, In 2o 3, Al 2o 3and TiO 2mixture, Lu in mixture 2o 3, In 2o 3, Al 2o 3and TiO 2mol ratio be 1:1:1:1;
(10) by the ZrO of step 9) 2powder and stablizer mixing and ball milling, the speed of ball milling is 280r/min, and the time of described ball milling is 2h;
(11) mixing material that step 10) is obtained being made base substrate through isostatic cool pressing, is then sinter 3.5h in the retort furnace of 1550 DEG C to make polynary stabilizing zirconia target in temperature;
(12) again target is put into L2 type electro beam physics vapour deposition equipment crucible, target size is Φ 70mm × 100mm, then with the high-power electron beam that power is 65KW, target is melted, target evaporates, the target atom of evaporation to deposit to above target through pretreated substrate surface, forms the anti-fused salt corrosion thermal barrier coating of polynary stabilizing zirconia.
embodiment 3
A, nano level ZrO 2the preparation of powder
(1) with ZrO (NO 3) 2as the zirconates raw material preparing Zirconium powder, with Y (NO 3) 36H 2o, as stablizer raw material, takes the ZrO (NO of 60g 3) 2with the Y (NO of 10g 3) 36H 2o, mixing;
(2) ZrO (NO will mixed 3) 2with Y (NO 3) 36H 2o joins in the deionized water of 500 ml, is uniformly mixed, filters, then adds 200ml ethanol, continues to be uniformly mixed;
(3) in step 2) add 7 ~ 9ml methane amide again in obtained solution, stir 35min;
(4) then in the solution of step 3), add 170ml 1,2 epoxy prapane again, dropping limit, limit is stirred;
(5) pour in culture dish, with preservative film sealing, be placed in pallet, the baking oven putting into 60 DEG C carries out gelation and ageing process, obtains wet gel;
(6) gel seal room temperature is placed 24 h, smash to pieces, be positioned in 110 DEG C of thermostatic drying chambers and dry;
(7) xerogel is moved into crucible, thermal treatment in 600 DEG C of retort furnaces, obtains presoma;
(8) again by presoma respectively 700 DEG C, 800 DEG C, 1000 DEG C and 1200 DEG C of thermal treatments, obtain the ZrO of nano level bigger serface 2powder;
B, prepare thermal barrier coating
(9) choose by step 1)-8) ZrO of 30g for preparing 2powder, then the stablizer choosing 6g, described stablizer is Lu 2o 3, In 2o 3, Al 2o 3and TiO 2mixture, Lu in mixture 2o 3, In 2o 3, Al 2o 3and TiO 2mol ratio be 1:1:1:1;
(10) by the ZrO of step 9) 2powder and stablizer mixing and ball milling, the speed of ball milling is 290r/min, and the time of described ball milling is 2h;
(11) mixing material that step 10) is obtained being made base substrate through isostatic cool pressing, is then sinter 3h in the retort furnace of 1600 DEG C to make polynary stabilizing zirconia target in temperature;
(12) again target is put into L2 type electro beam physics vapour deposition equipment crucible, target size is Φ 70mm × 100mm, then with the high-power electron beam that power is 65KW, target is melted, target evaporates, the target atom of evaporation to deposit to above target through pretreated substrate surface, forms the anti-fused salt corrosion thermal barrier coating of polynary stabilizing zirconia.
Embodiment 1-3 and traditional YSZ heat barrier coat material are carried out contrast experiment, passes through at 900 DEG C, 60mg/cm 2the Na of concentration 2sO 4-V 2o 5carry out corrosion resistance test in fused salt, net result shows the anti-Na of the polynary stabilizing zirconia of the present invention anti-fused salt corrosion heat barrier coat material 2sO 4-V 2o 5the fused salt corrosion life-span improves more than 8 times than traditional thermal barrier material.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention; the technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and application claims protection domain is defined by appending claims and equivalent thereof.

Claims (5)

1. one kind is passed through the standby ZrO of electro beam physics vapour deposition legal system 2thermal barrier coating, is characterized in that, this ZrO 2thermal barrier coating comprises following raw material:
The bigger serface stabilized nanoscale ZrO of 30 ~ 35g 2powder,
The stablizer of 4 ~ 6g;
Wherein, described stablizer is Lu 2o 3, In 2o 3, Al 2o 3and TiO 2mixture, Lu in mixture 2o 3, In 2o 3, Al 2o 3and TiO 2mol ratio be 1:1:1:1
Wherein, described bigger serface stabilized nanoscale ZrO 2powder is prepared by following raw material and step:
(1) ZrO (NO is chosen 3) 2as the zirconates raw material preparing Zirconium powder, choose Y (NO 3) 36H 2o, as stablizer raw material, takes the ZrO (NO of 55 ~ 60g 3) 2with the Y (NO of 10 ~ 12g 3) 36H 2o, fully mixes;
(2) ZrO (NO step 1) mixed 3) 2with Y (NO 3) 36H 2o mixture joins in the deionized water of 450 ~ 500 ml, is uniformly mixed, filters, then adds 190 ~ 200ml ethanol, continues to be uniformly mixed;
(3) in step 2) add 7 ~ 9ml methane amide again in obtained solution, stir 25 ~ 35min;
(4) then in the solution of step 3), add 165 ~ 170ml 1,2 epoxy prapane again, dropping limit, limit is stirred;
(5) pour in culture dish, with preservative film sealing, be placed in pallet, the baking oven putting into 60 DEG C carries out gelation and ageing process, obtains wet gel;
(6) gel seal room temperature is placed 24 h, smash to pieces, be positioned in 110 DEG C of thermostatic drying chambers and dry;
(7) xerogel is moved into crucible, thermal treatment in 600 DEG C of retort furnaces, obtains presoma;
(8) again by presoma respectively 700 DEG C, 800 DEG C, 1000 DEG C and 1200 DEG C of thermal treatments, obtain the ZrO of nano level bigger serface 2powder;
And,
Above-mentioned thermal barrier coating is prepared by following steps:
By the bigger serface stabilized nanoscale ZrO of 30 ~ 35g 2the stablizer mixing and ball milling of powder and 4 ~ 6g, the speed of ball milling is 270 ~ 290r/min, and the time of described ball milling is 2h;
Obtained mixing material is made base substrate through isostatic cool pressing, is then sinter 3 ~ 4h in the retort furnace of 1500 ~ 1600 DEG C to make polynary stabilizing zirconia target in temperature;
Target is put into electro beam physics vapour deposition equipment crucible again, with high-power electron beam, target is melted, target evaporates, and the target atom of evaporation to deposit to above target through pretreated substrate surface, forms the anti-fused salt corrosion thermal barrier coating of polynary stabilizing zirconia.
2. ZrO according to claim 1 2thermal barrier coating, is characterized in that, prepares bigger serface stabilized nanoscale ZrO 2the step 2 of powder) in plasma water addition be preferably 480ml.
3. ZrO according to claim 1 and 2 2thermal barrier coating, is characterized in that, bigger serface stabilized nanoscale ZrO 2powder is preferably 32g, and stablizer is preferably 5g.
4. according to the ZrO of claim 1 2thermal barrier coating, is characterized in that, the speed of ball milling is preferably 280r/min.
5. ZrO according to claim 1 2thermal barrier coating, is characterized in that, described electro beam physics vapour deposition equipment is L2 type electro beam physics vapour deposition equipment, and target size is Φ 70mm × 100mm.
CN201310181530.6A 2013-05-16 2013-05-16 ZrO2 thermal barrier coating prepared by electron-beam physical vapor desorption Expired - Fee Related CN103225062B (en)

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