CN103290352A - Method for preparing zirconium oxide thermal barrier coating by spraying process - Google Patents
Method for preparing zirconium oxide thermal barrier coating by spraying process Download PDFInfo
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Abstract
The invention relates to a method for preparing a zirconium oxide thermal barrier coating by a spraying process, which comprises the following steps: preparing large-specific-area stable nano zirconium oxide powder by a green environment-friendly process; and on the basis of the prepared large-specific-area stable nano zirconium oxide powder, adding proper amounts of Lu2O3, In2O3, Al2O3 and TiO2 to prepare the ZrO2 thermal barrier coating. The prepared coating has the advantages of high stability and high corrosion resistance.
Description
Technical field
The invention belongs to materials science field, be specifically related to the method that a kind of spraying method prepares Zirconium oxide heat 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, make and at high temperature to move with its device of making (as the engine turbine blade), and can improve device (engine etc.) thermo-efficiency and reach more than 60%.
U.S. NASA (National Aeronautics and Space Administration)-high temperature resistance and the corrosion resistance nature of Lewis research centre in order to improve gas-turbine blade, rocket engine has just proposed the thermal barrier coating concept fifties as far back as twentieth century.Select and after preparation technology carries out the exploration of long period, obtained important breakthrough the beginning of the eighties, for solid foundation has been established in the application of thermal barrier coating at the material of coating.Document shows that present advanced thermal barrier coating can reduce about high-temperature engine hot-end component temperature 170K under Working environment.Along with the application of thermal barrier coating on the high-temperature engine hot-end component, people recognize that the application of thermal barrier coating not only can reach the matrix resistance to high temperature corrosion ability that improves, further improve the purpose of engine operating temperature, and can reduce fuel oil consumption, raise the efficiency, prolong work-ing life of hot-end component.Compare with the development of new high temperature alloy, the research cost of thermal barrier coating is relatively low, and technology is also real feasible.
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 limit situation of reach a high temperature alloy and monocrystal material.Be example with the heating part of fuel turbine such 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 has surpassed the ultimate temperature (1075 ℃) that high temperature nickel alloy is used up to 1100 ℃.The high strength of metal, high tenacity and pottery resistant to elevated temperatures combined prepared thermal barrier coating a little can be addressed the above problem, it can play heat insulation, anti-oxidant, etch-proof effect, obtain certain application at hot junction materials such as steam turbine, oil electric engine, jet engines, and improved the work-ing life of hot-end component.
Zirconium dioxide is the main raw material in the present thermal barrier coating, and zirconium dioxide (chemical formula: ZrO2, or claim zirconium white) be the main oxides of zirconium, be white odorless, tasteless crystal under the usual condition, be insoluble in water, hydrochloric acid and dilute sulphuric acid.General normal a spot of hafnium oxide that contains.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 ℃.It can improve the high temperature viscosity of glaze and enlarge the temperature range that viscosity changes, and thermostability is preferably arranged, and when its content is 2%-3%, can improve the freedom from cracking performance of glaze.Also the unreactiveness because of it is big, so can improve chemical stability and the acid and alkali-resistance ability of glaze, can also play the effect of opacifying agent. and the zircons that use in the architectural pottery glaze, general consumption is 8%-12% more.And be the main raw material of " under the glaze white ", zirconium white be yellow-green pigment good help toner, must select the pure zirconium white of matter for use if want to obtain preferably vanadium zirconium yellow pigment.
The chemical property of zirconium dioxide is very stable, and the zirconium dioxide character after calcining is torpescence especially.It can be corroded by hot concentrated hydrochloric acid, sulfuric acid, hydrofluoric acid and nitric acid, can generate zirconate with oxyhydroxide, oxide compound and carbonate congruent melting under the high temperature, comes down to high molecular mixed metal oxide.Zirconium dioxide and carbon and chlorine pyroreaction perhaps with carbon tetrachloride reaction, generate zirconium tetrachloride and zirconyl chloride, the hydrolysis zirconium dioxide of getting back.It generates zirconium carbide with the carbon effect in electric arc.
The preparation method of zirconium dioxide is more, and wherein the sol-gel method in the wet chemistry method is because the trickle and narrowly distributing of material particle size of preparation; The material purity height, the chemical ingredients that obtain are even; Firing temperature is present comparatively ideal and the method for preparing the zirconium dioxide powder with practical value than advantages such as low 400 ℃-500 ℃ of traditional methods.
From french chemist J.J.Ebelmen SiCl in 1846
4After ethanol mixes, find hydrolysis to take place in wet air and formed gel.Colloidal sol-gel technique progressively improves and has obtained tremendous development in 100 years.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 that is difficult to make in glass, ultrafine powder, oxide coating, fiber, function ceramics powder and the traditional method application of succeeding.
Sol-gel process is one of wet-chemical reaction method, usually make presoma with metal alkoxide or inorganic salt, under liquid phase, these raw materials are evenly mixed, and be hydrolyzed, the condensation chemical reaction, form stable vitreosol system in solution, colloidal sol is slowly polymerization through between the ageing micelle, forms the gel of three-dimensional space network structure, be full of the solvent that loses flowability between gel network, formed gel.Gel is prepared the material of molecule and even nanometer substructure through super-dry, sintering curing.
Solvation:
M(H2O)nz+=M(H2O)n-1(OH)(z-1)+H
+
Hydrolysis reaction:
M(OR)n+xH2O=M(OH)x(OR)n-x+xROH------M(OH)n
Polycondensation:
Dehydration polycondensation :-M-OH+HO-M-=-M-O-M-+H2O
Lose pure polycondensation :-M-OR+HO-M-=-M-O-M-+ROH
Inorganic salt or metal alkoxide are made presoma, under liquid phase, these raw materials are evenly mixed, and be hydrolyzed, the condensation chemical reaction, or form colloidal sol with fixed attention by solution, the principal element that influences this process has the temperature of reaction of water, add-on, rate of addition, pH etc.The raising of temperature helps the hydrolysis of alkoxide, to the alkoxide low to hydrolytic activity (as silicon alkoxide), its hydrolysis often needs to carry out under heating state, be that water speed increases the increase of micelle molecular kinetic energy, probability of collision also increases, rate of polymerization is fast, thereby cause the colloidal sol time to shorten, on the other hand, the volatilization of solvent alcohol is also accelerated under the comparatively high temps, is equivalent to increase reactant concn, it is also unsuitable too high also to have accelerated colloidal sol speed simultaneous temperature to a certain extent, too high temperature can make the colloidal sol of generation unstable relatively, and the hydrolytic-polymeric reaction of multiple product is easily arranged, and generates not volatile organic matter.Therefore guaranteeing to generate under the situation of colloidal sol, take lesser temps as far as possible.The add-on of water should add according to stoichiometric ratio.The collagen amount that stoichiometric ratio adds is good, becomes the time of glue shorter relatively.If being lower than the needed consumption of stoichiometric ratio, amount of water can make alcoholization hydrolysis reaction speed slack-off and prolong the colloidal sol time; If amount of water is higher than in the needed consumption of stoichiometric ratio solution becomes must be diluted, soltion viscosity descends, and becomes glue difficult.When dripping alkoxide solution, should under the situation of other term harmonizations, observe rate of addition, drop rate is more fast, gelation rate is also fast, but rate of addition is too fast, can make the too fast generation polymerization of local hydrolysis gelling generate precipitation, and the gel that hydrolysis finally can't obtain homogeneous does not take place a part of sol solutions simultaneously, so when reaction, also should be aided with even stirring, thereby guarantee the gel that acquisition is evenly distributed.The pH difference of reaction solution, its reaction mechanism difference, thereby to the hydrolytie polycondensation with a kind of metal alkoxide often produces structure, polycondensation that form is different.Studies show that, pH hour, polycondensation speed is far longer than hydrolysis reaction, hydrolysis is by H
+Close motor reason cause that polycondensation begins before complete hydrolysis, so the polycondensate degree of crosslinking is low; When pH was big, the hydrolysis reaction system of system was by [OH
-] nucleophilic substitution cause that hydrolysis rate is greater than nucleophilic speed, form high polymer, higher degree of crosslinking is arranged, can select suitable acid base catalysator by the material requirements that specifically will produce.
Form stable vitreosol system in solution, colloidal sol is slowly polymerization through between the ageing micelle, forms the gel of three-dimensional space network structure, and the colloidal sol of tool flowability forms the gelling system that can not flow after polycondensation.The sol solution that forms through polycondensation is during in ageing, and polymkeric substance is further assembled and grown up into the granule submanifold, and they collide mutually and connect into macroparticle bunch, and simultaneously, liquid phase is wrapped in and loses mobilely in the solid phase skeleton, forms gel.Be full of the solvent that loses flowability between gel network, formed gel.Gel is prepared the material of molecule and even nanostructure through super-dry, sintering curing and subsequent heat treatment.It is the novel method that the preparation nano material is commonly used and convenient and easy, do not need severe condition.
Yet the metal alkoxide that adopts usually in the prior art is as organic method of presoma, though preparing product has the ultra-fine ZrO2 powder of bigger serface, this method cost is higher, and the zirconium alkoxide is expensive, is difficult for realizing suitability for industrialized production.Prior art also has avoids using expensive alkoxide, and the oxalic acid that adopts decomposition can not produce obnoxious flavour is precipitation agent, has also prepared the ZrO2 nano-powder.The sol-gel method of this modification adds the tensio-active agent that molecular weight varies in size before coagulation, adopt the dehydrated alcohol ultra-sonic dispersion behind the coagulation, can eliminate agglomeration effectively, however numerous and diverse according to this method preparation process, and amount of surfactant is difficult to control, and production cost is higher.The problem demanding prompt solution that become free from environmental pollution again when therefore how to prepare bigger serface stabilized nanoscale ZrO2 powder.
In addition, people confirm that by a large amount of tests the main medium that the gas turbine engine that scribbles thermal barrier coating is produced the thermal etching effect is NaCl, Na
2SO
4, V
2O
5Deng.Under different condition, 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 atmosphere or seawater, especially at sea or the aircraft of operation in the coastal atmospheric environment.Na
2SO
4And V
2O
5Not directly from atmosphere.Na
2SO
4Mainly the combustion oxidation from sulphur in the rocket engine fuel and compound thereof reacts.The preparation thermal barrier coating technology in, in the prior art usually with Y
2O
3, Ta
2O
5, Nd
2O
3Or or La
2O
3As stabilizer element, the thermal etching that impurity chemical reactions at high temperature such as the vanadic salts in mentioned component and the oil plant, sodium salt cause also is the common factor that causes coating to lose efficacy.The corrosion fused salt penetrates into coating by the hole in the plasma spraying coating under the high temperature, 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 lost efficacy the thermal barrier coating unsticking.
Summary of the invention
The purpose of this invention is to provide the method that a kind of spraying method prepares Zirconium oxide heat barrier coating, main purpose is on the basis of prepared bigger serface stabilized nanoscale Zirconium powder, adds an amount of Lu
2O
3, In
2O
3, Al
2O
3And TiO
2Prepare the ZrO2 thermal barrier coating, prepared coating good stability and have higher corrosion resistance.
Goal of the invention of the present invention is achieved through the following technical solutions: a kind of spraying method prepares the method for Zirconium oxide heat barrier coating, comprises following steps:
The preparation of A, nano level ZrO2 powder
(1) takes by weighing the Zr (OH) of 230～250 weight parts
4YCl with 27～33 weight parts
3, joining and being mixed with concentration in the deionized water is 6% acidic solution, is heated to 65 ℃ under agitation condition, fully dissolving and fully mixing;
(2) get the potassium hydroxide of 660 ~ 690 weight parts, join and be mixed with 13% basic solution in the deionized water, at the uniform velocity be added drop-wise to the acidic solution that is mixed with in the above-mentioned steps in the basic solution, regulating the pH value is 9.3 ~ 9.5, make two kinds of salt co-precipitation, obtain having the yttria-stabilized zirconia of crystal water, heavyization 3h obtains hydrogel;
(3) in the hydrogel of above-mentioned steps preparation, add dispersion agent and filter except the alkaline agent making beating, with the Zr behind the deionized water wash (OH)
4Hydrogel AgNO
3Check is until detecting less than Cl
-
(4) filter cake after will filtering adds tertiary amyl alcohol and stirs 30min, the volume ratio 1:5 of filter cake and alcohol;
(5) continue when being warming up to 95 ~ 98 ℃, to carry out dynamic component distillation, the zirconium hydroxide powder that obtains loosening;
(6) continue behind 550 ~ 700 ℃ of following high-temperature calcination 1.5 ~ 2h, 5 ℃/min of temperature rise rate obtains the ZrO2 powder of nano level bigger serface;
B, preparation thermal barrier coating
(7) choose the ZrO2 powder of the nano level bigger serface of 90～110 weight parts by above-mentioned steps preparation, choose the stablizer of 12～15 weight parts again, described stablizer is Lu
2O
3, In
2O
3, Al
2O
3And TiO
2Mixture, Lu in the mixture
2O
3, In
2O
3, Al
2O
3And TiO
2Mol ratio be 1:1:1:1;
(8) ZrO2 powder and stablizer mixing and ball milling that proportioning in the above-mentioned steps is good, the speed of ball milling is 270～290r/min, the time of described ball milling is 2h;
(9) form the high temperature and high speed plasma jet by plasma gun, after the mixed powder that powder feeding air-flow promotion above-mentioned steps makes enters plasma jet, mixed powder is heated to fusion or semi-melting state rapidly, and accelerated by plasma jet, the spraying particle bundle of base material is flown in formation, particle beam strikes through pretreated substrate surface, forms thermal barrier coating at last.
Further, dispersion agent adopts PEG4000, and add-on is 0.03% of slip weight, and except alkaline agent is oxalic acid, add-on is 0.8% of slip weight.
About technique effect of the present invention.At first, mix with reaction process in, the zirconium white nucleus just begins to take shape, just can grow up through Overheating Treatment forms cubic phase stabilized nanoscale Zirconium powder.Because do not occur normal chlorion, the sulfonium ion problem that exists in the liquid phase method in the reaction product, thereby the cleaning of product is easy, powder is loose, it is few to reunite, the reactive behavior height, and specific surface area is long-pending big, Heat stability is good.Then, when the preparation thermal barrier coating, owing to selected Lu
2O
3, In
2O
3, Al
2O
3And TiO
2Mixture as stablizer, when the spraying particle bundle, host (ZrO in the particle beam
2) and stablizer (Lu
2O
3, In
2O
3, Al
2O
3With TiO
2) between spread, form Lu
2O
3, In
2O
3, Al
2O
3With TiO
2Impurity ZrO
2Particle beam, particle beam strikes through pretreated substrate surface, finally forms Lu
2O
3, In
2O
3, Al
2O
3With TiO
2Polynary stabilizing zirconia (four directions is mutually with metastable mutually cubic) corrosion and heat resistant coating.Because Lu
5+, In
3+, Al
3+And Ti
4+Ionic radius less than Na
2SO
4-V
2O
5V in the fused salt
5+Ionic radius, and Lu
5+With In
3+The defective combined action increased In
2O
3Anti-Na
2SO
4-V
2O
5Fused salt corrosion performance, so stablizer Lu
2O
3, In
2O
3, Al
2O
3And TiO
2All and Na
2SO
4-V
2O
5Fused salt is difficult to take place chemical reaction.So the polynary stabilizing zirconia corrosion and heat resistant of the present invention coated material has excellent stability and anti-fused salt corrosion performance.Above-mentioned preparation method there is no report in the prior art.
To sum up, the thermal barrier coating preparation process of the present invention's preparation 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
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
The preparation of A, nano level ZrO2 powder
(1) takes by weighing the Zr (OH) of 230 weight parts
4YCl with 33 weight parts
3, joining and being mixed with concentration in the deionized water is 6% acidic solution, is heated to 65 ℃ under agitation condition, fully dissolving and fully mixing;
(2) get the potassium hydroxide of 660 weight parts, join and be mixed with 13% basic solution in the deionized water, at the uniform velocity be added drop-wise to the acidic solution that is mixed with in the above-mentioned steps in the basic solution, regulating the pH value is 9.4, make two kinds of salt co-precipitation, obtain having the yttria-stabilized zirconia of crystal water, heavyization 3h obtains hydrogel;
(3) in the hydrogel of above-mentioned steps preparation, add dispersion agent and filter except the alkaline agent making beating, with the Zr behind the deionized water wash (OH)
4Hydrogel AgNO
3Check is until detecting less than Cl
-Dispersion agent adopts PEG4000, and add-on is 0.03% of slip weight, and except alkaline agent is oxalic acid, add-on is 0.8% of slip weight;
(4) filter cake after will filtering adds tertiary amyl alcohol and stirs 30min, the volume ratio 1:5 of filter cake and alcohol;
(5) continue when being warming up to 97 ℃, to carry out dynamic component distillation, the zirconium hydroxide powder that obtains loosening;
(6) continue behind 550 ℃ of following high-temperature calcination 2h, 5 ℃/min of temperature rise rate obtains the ZrO2 powder of nano level bigger serface;
B, preparation thermal barrier coating
(7) choose the ZrO2 powder of the nano level bigger serface of 90 weight parts by above-mentioned steps preparation, choose the stablizer of 15 weight parts again, described stablizer is Lu
2O
3, In
2O
3, Al
2O
3And TiO
2Mixture, Lu in the mixture
2O
3, In
2O
3, Al
2O
3And TiO
2Mol ratio be 1:1:1:1;
(8) ZrO2 powder and stablizer mixing and ball milling that proportioning in the above-mentioned steps is good, the speed of ball milling is 270r/min, the time of described ball milling is 2h;
(9) form the high temperature and high speed plasma jet by plasma gun, after the mixed powder that powder feeding air-flow promotion above-mentioned steps makes enters plasma jet, mixed powder is heated to fusion or semi-melting state rapidly, and accelerated by plasma jet, the spraying particle bundle of base material is flown in formation, particle beam strikes through pretreated substrate surface, forms thermal barrier coating at last.
Embodiment 2
The preparation of A, nano level ZrO2 powder
(1) takes by weighing the Zr (OH) of 240 weight parts
4YCl with 29 weight parts
3, joining and being mixed with concentration in the deionized water is 6% acidic solution, is heated to 65 ℃ under agitation condition, fully dissolving and fully mixing;
(2) get the potassium hydroxide of 680 weight parts, join and be mixed with 13% basic solution in the deionized water, at the uniform velocity be added drop-wise to the acidic solution that is mixed with in the above-mentioned steps in the basic solution, regulating the pH value is 9.3, make two kinds of salt co-precipitation, obtain having the yttria-stabilized zirconia of crystal water, heavyization 3h obtains hydrogel;
(3) in the hydrogel of above-mentioned steps preparation, add dispersion agent and filter except the alkaline agent making beating, with the Zr behind the deionized water wash (OH)
4Hydrogel AgNO
3Check is until detecting less than Cl
-Dispersion agent adopts PEG4000, and add-on is 0.03% of slip weight, and except alkaline agent is oxalic acid, add-on is 0.8% of slip weight;
(4) filter cake after will filtering adds tertiary amyl alcohol and stirs 30min, the volume ratio 1:5 of filter cake and alcohol;
(5) continue when being warming up to 98 ℃, to carry out dynamic component distillation, the zirconium hydroxide powder that obtains loosening;
(6) continue behind 600 ℃ of following high-temperature calcination 2h, 5 ℃/min of temperature rise rate obtains the ZrO2 powder of nano level bigger serface;
B, preparation thermal barrier coating
(7) choose the ZrO2 powder of the nano level bigger serface of 100 weight parts by above-mentioned steps preparation, choose the stablizer of 13 weight parts again, described stablizer is Lu
2O
3, In
2O
3, Al
2O
3And TiO
2Mixture, Lu in the mixture
2O
3, In
2O
3, Al
2O
3And TiO
2Mol ratio be 1:1:1:1;
(8) ZrO2 powder and stablizer mixing and ball milling that proportioning in the above-mentioned steps is good, the speed of ball milling is 280r/min, the time of described ball milling is 2h;
(9) form the high temperature and high speed plasma jet by plasma gun, after the mixed powder that powder feeding air-flow promotion above-mentioned steps makes enters plasma jet, mixed powder is heated to fusion or semi-melting state rapidly, and accelerated by plasma jet, the spraying particle bundle of base material is flown in formation, particle beam strikes through pretreated substrate surface, forms thermal barrier coating at last.
Embodiment 3
The preparation of A, nano level ZrO2 powder
(1) takes by weighing the Zr (OH) of 250 weight parts
4YCl with 27 weight parts
3, joining and being mixed with concentration in the deionized water is 6% acidic solution, is heated to 65 ℃ under agitation condition, fully dissolving and fully mixing;
(2) get the potassium hydroxide of 690 weight parts, join and be mixed with 13% basic solution in the deionized water, at the uniform velocity be added drop-wise to the acidic solution that is mixed with in the above-mentioned steps in the basic solution, regulating the pH value is 9.5, make two kinds of salt co-precipitation, obtain having the yttria-stabilized zirconia of crystal water, heavyization 3h obtains hydrogel;
(3) in the hydrogel of above-mentioned steps preparation, add dispersion agent and filter except the alkaline agent making beating, with the Zr behind the deionized water wash (OH)
4Hydrogel AgNO
3Check is until detecting less than Cl
-Dispersion agent adopts PEG4000, and add-on is 0.03% of slip weight, and except alkaline agent is oxalic acid, add-on is 0.8% of slip weight;
(4) filter cake after will filtering adds tertiary amyl alcohol and stirs 30min, the volume ratio 1:5 of filter cake and alcohol;
(5) continue when being warming up to 95 ℃, to carry out dynamic component distillation, the zirconium hydroxide powder that obtains loosening;
(6) continue behind 700 ℃ of following high-temperature calcination 1.5h, 5 ℃/min of temperature rise rate obtains the ZrO2 powder of nano level bigger serface;
B, preparation thermal barrier coating
(7) choose the ZrO2 powder of the nano level bigger serface of 90～110 weight parts by above-mentioned steps preparation, choose the stablizer of 12～15 weight parts again, described stablizer is Lu
2O
3, In
2O
3, Al
2O
3And TiO
2Mixture, Lu in the mixture
2O
3, In
2O
3, Al
2O
3And TiO
2Mol ratio be 1:1:1:1;
(8) ZrO2 powder and stablizer mixing and ball milling that proportioning in the above-mentioned steps is good, the speed of ball milling is 290r/min, the time of described ball milling is 2h;
(9) form the high temperature and high speed plasma jet by plasma gun, after the mixed powder that powder feeding air-flow promotion above-mentioned steps makes enters plasma jet, mixed powder is heated to fusion or semi-melting state rapidly, and accelerated by plasma jet, the spraying particle bundle of base material is flown in formation, particle beam strikes through pretreated substrate surface, forms thermal barrier coating at last.
Embodiment 1-3 and traditional YSZ heat barrier coat material are compared experiment, through at 900 ℃, 60mg/cm
2The Na of concentration
2SO
4-V
2O
5Carry out the corrosion resistance test in the fused salt, net result shows the anti-Na of the anti-fused salt corrosion heat barrier coat material of the polynary stabilizing zirconia of the present invention
2SO
4-V
2O
5The fused salt corrosion life-span has improved more than 8 times than traditional thermal barrier material.
More than show and described 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; that describes in above-described embodiment and the 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 the claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (4)
1. a spraying method prepares the method for Zirconium oxide heat barrier coating, comprises following steps:
The preparation of A, nano level ZrO2 powder
(1) takes by weighing the Zr (OH) of 230～250 weight parts
4YCl with 27～33 weight parts
3, joining and being mixed with concentration in the deionized water is 6% acidic solution, is heated to 65 ℃ under agitation condition, fully dissolving and fully mixing;
(2) get the potassium hydroxide of 660 ~ 690 weight parts, join and be mixed with 13% basic solution in the deionized water, at the uniform velocity be added drop-wise to the acidic solution that is mixed with in the above-mentioned steps in the basic solution, regulating the pH value is 9.3 ~ 9.5, make two kinds of salt co-precipitation, obtain having the yttria-stabilized zirconia of crystal water, heavyization 3h obtains hydrogel;
(3) in the hydrogel of above-mentioned steps preparation, add dispersion agent and filter except the alkaline agent making beating, with the Zr behind the deionized water wash (OH)
4Hydrogel AgNO
3Check is until detecting less than Cl
-
(4) filter cake after will filtering adds tertiary amyl alcohol and stirs 30min, the volume ratio 1:5 of filter cake and alcohol;
(5) continue when being warming up to 95 ~ 98 ℃, to carry out dynamic component distillation, the zirconium hydroxide powder that obtains loosening;
(6) continue behind 550 ~ 700 ℃ of following high-temperature calcination 1.5 ~ 2h, 5 ℃/min of temperature rise rate obtains the ZrO2 powder of nano level bigger serface;
B, preparation thermal barrier coating
(7) choose the ZrO2 powder of the nano level bigger serface of 90～110 weight parts by above-mentioned steps preparation, choose the stablizer of 12～15 weight parts again, described stablizer is Lu
2O
3, In
2O
3, Al
2O
3And TiO
2Mixture, Lu in the mixture
2O
3, In
2O
3, Al
2O
3And TiO
2Mol ratio be 1:1:1:1;
(8) ZrO2 powder and stablizer mixing and ball milling that proportioning in the above-mentioned steps is good, the speed of ball milling is 270～290r/min, the time of described ball milling is 2h;
(9) form the high temperature and high speed plasma jet by plasma gun, after the mixed powder that powder feeding air-flow promotion above-mentioned steps makes enters plasma jet, mixed powder is heated to fusion or semi-melting state rapidly, and accelerated by plasma jet, the spraying particle bundle of base material is flown in formation, particle beam strikes through pretreated substrate surface, forms thermal barrier coating at last.
2. the method for preparing the ZrO2 thermal barrier coating according to claim 1 is characterized in that, dispersion agent adopts PEG4000, and add-on is 0.03% of slip weight.
3. prepare the method for Zirconium oxide heat barrier coating according to claim 1 and 2 described spraying methodes, it is characterized in that, except alkaline agent is oxalic acid, add-on is 0.8% of slip weight.
4. prepare the method for Zirconium oxide heat barrier coating according to the spraying method of claim 1-3, it is characterized in that, the speed of the ball milling in the above-mentioned steps is preferably 280r/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310240992.0A CN103290352B (en) | 2013-06-18 | 2013-06-18 | A kind of spraying method prepares the method for Zirconium oxide heat barrier coating |
Applications Claiming Priority (1)
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| CN113403567A (en) * | 2021-06-25 | 2021-09-17 | 西安热工研究院有限公司 | Nano yttrium oxide stabilized zirconia thermal barrier coating and preparation method thereof |
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| CN117088686A (en) * | 2023-10-19 | 2023-11-21 | 沈阳恒泰鑫源精铸耐材有限公司 | Modified zirconia coating and preparation method thereof |
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