CN101200375A - Preparation method of nano zirconium-containing series thermal barrier coating material - Google Patents
Preparation method of nano zirconium-containing series thermal barrier coating material Download PDFInfo
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Abstract
A method for preparing a nano zirconium-containing series thermal barrier coating material. Preparing zirconium carbonate or basic zirconium carbonate by using cheap zirconium oxychloride and ammonium carbonate or ammonium bicarbonate as raw materials, mixing the zirconium carbonate or basic zirconium carbonate with one or more of hydroxides of alkaline earth metals, rare earth metals, titanium and aluminum, carbonate precipitates or other compounds according to requirements, and obtaining the nano zirconium oxide ZrO doped with different substances after stirring, ball milling, spray drying, granulation and heat treatment processes2Or pyrochlore crystal structure nano rare earth zirconate RE2Zr2O7And (3) an agglomerated nanometer powder product. The preparation method has the advantages of strong adaptability, short flow, easy scale production, mild preparation technical conditions, low production cost and good product quality, is favorable for obtaining porous agglomerated zirconium-containing nano compound particle powder, and is suitable for preparing materials of thermal barrier coatings.
Description
[technical field]: the invention belongs to technical field of inorganic nonmetallic materials.Relate to method for preparing nano zirconium-containing series thermal barrier coating material, especially relate to doped zirconia and have pyrochlore-type crystalline structure rare earth zirconate RE
2Zr
2O
7Etc. preparation of nanomaterials.
[background technology]: aircraft engine develops to high flow capacity ratio, high thrust-weight ratio, high turbine air inlet temperature direction in recent years, the engine thermal end pieces, particularly the fuel gas temperature of combustion chamber and gaseous-pressure improve constantly, the flight velocity of modern supersonic aircraft has met or exceeded 4 overtone speed, the temperature of inlet air of aircraft engine has reached 1300 ℃, along with the performance of engine improves constantly, expectation will reach 1700 ℃, even may be at 2000 ℃.High like this temperature far surpasses the fusing point of existing alloy.Therefore,, must take corresponding measure for reaching so high fuel gas temperature, the one, improve cooling technology, to reduce the temperature of combustion chamber wall and contacts fuel gas, for example adopt and press layered structure, air film cooling technology; Two are to use more advanced high temperature alloy; The 3rd, on existing refractory alloy, spray thermal barrier coating (Thermal Barrier Coatings, TBCs).No matter water-cooled still is the air film cooling technology to adopt cooling technology, if adopt too much inside and outside cooling, will reduce the thermo-efficiency of engine, all can increase energy consumption undoubtedly, and causes motor performance to descend.
Simultaneously, it is very limited further to excavate the potentiality of high temperature alloy working temperature.Therefore improving the feasible and the most most economical approach of thermal engine working temperature, is under the prerequisite of using more advanced high temperature alloy and cooling technology, further reduces the thermal conductivity of TBCs ceramic coating material.
Thermal barrier coating is one of gordian technique of modern aeroengine, and its ultimate principle is based on ceramic coating and has high fusing point and low thermal conductivity, and ceramic coating contains suitable porosity in addition, thereby makes heat barrier ceramic coating become good high temperature thermal insulation material.It can come the high-temperature component of jet engine and internal combustion turbine and high-temperature fuel gas are isolated.Its main effect is the working temperature that has reduced hot-end component, prevents parts generation high temperature corrosion, has improved the service temperature and the thermo-efficiency of aircraft engine, has reduced free air delivery, has saved fuel, has prolonged the work-ing life of workpiece.
The application of thermal barrier coating can reduce the working temperature of component materials such as turbine engine combustion chamber, thereby increases substantially its performance, life-span and reliability, reduces the specific fuel oil consumption of engine.The research emphasis of various countries all is placed in the research of heat barrier coat material now, and NASA (NASA) just classifies the hot junction technology of aircraft engine as the primary study project specially in the eighties in 20th century.Thermal barrier coating has easily manufacturing of parts, less investment, cost is low, safe and reliable and easily overhaul, easy advantage such as replacing, TBCs is that aircraft engine and internal combustion turbine industry have brought great improvement and benefit.Therefore, man of World Airways engine shop all attaches great importance to the exploitation of heat barrier coat material and technology of preparing.
Typical thermal barrier coating system is to be made of the corrosion-resistant tack coat and the surface ceramic layer that are coated on the superalloy substrate.Zirconium white (ZrO
2) be one of best, the most frequently used upper layer stupalith of performance, but pure ZrO
2To cryogenic transformation tangible lag-effect is arranged from high temperature, and occur about 4% volumetric expansion when changing, cause ZrO
2Crack, even burst phenomenon.Therefore, pure ZrO
2Use less.In order to prevent the conversion of low temperature crystal formation and high temperature crystal formation, generally need to add some CaO, MgO, Y
2O
3, CeO, Yb
2O
3, Er
2O
3, Dy
2O
3, Gd
2O
3, Eu
2O
3Deng as the crystalline structure stablizer.6～8%wt%Y wherein
2O
3Partially stabilized ZrO
2(P-YSZ) ceramic topcoats is used the most general.
At present, in order to satisfy the service requirements of higher temperature (greater than 1200 ℃) thermal barrier coating, people are just at the Development of New Generation heat barrier coat material, comprising having pyrochlore-type crystalline structure (A
2B
2O
7) the zirconate material, as rare earth zirconate RE
2Zr
2O
7(RE=Y, La, Ce, Nd, Sm, Eu, Gd, Dy, Er, Yb etc.).
Although the application of thermal barrier coating on aircraft engine is more prevalent, the actual effect of heat insulation of surface ceramic layer and disbonding problem affect thermal barrier coating applying on high-pressure turbine blade always.Because in a single day ceramic thermal barrier layer peels off, blade alloy is exposed to causes in the high-temperature fuel gas losing efficacy.In order further to improve the heat insulation and antistrip performance of thermal barrier coating, carried out number of research projects over past ten years both at home and abroad, from improving the angle of thermal barrier coating microtexture, design and developed such as continuous gradient coating, two-dirnentional structure coating, nano coating and little lamination etc.Wherein the nanometer thermal barrier coating is with its excellent heat-proof quality, high interfacial bonding strength, high strain tolerance limit and damage drag, becomes one of high-performance thermal barrier coating developing direction of tool potentiality.Nano structural material makes thermal barrier coating obtain high-ductility and toughness, high strength and hardness, high thermal expansion coefficient, and performances such as low density, low elastic modulus and lower thermal conductivity become possibility.Though the nanometer thermal barrier coating has a good application prospect, material and the cost of making coating are also limiting its widespread use.
Contriver marquis's book grace etc. has been applied for the preparation method of nano zirconium oxide powder, in containing the aqueous solution of zirconates, add alkaline precipitating agent, obtain precipitation of hydroxide, washing more after filtration,, dehydration, dry, calcining, obtain Zirconium powder, it is characterized in that adopting the colloidal solution after azeotropic distn dewaters dry in water distilling apparatus, constantly stir when dehydration and drying.Its application content is referring to " preparation method of nano zirconium oxide powder ", and publication number is CN1397597A.
Contriver marquis's book grace, Wang Yanxin, Xiang Longbin, Song Zihong, Chen Hao, king's equality have been applied for the yttrium stable zirconium oxide agglomerate type powder and the production method thereof of nanostructure.This method is to add entry in containing the nano zircite particle of yttrium oxide, obtains the aqueous suspension colloid, makes through spraying drying, screening, thermal treatment, plasma body densificationization again.Comprise the steps: yttrium stabilized nano level ZrO
2, powder granule mixes with water, is prepared into the water nano suspensoid; Adopt drying process with atomizing that the water nano suspensoid is made the micron order agglomerate type powder; Agglomerate type powder is heat-treated; Powder after adopting plasma technology to thermal treatment carries out densification, obtains the yttrium stable zirconium oxide agglomerate type powder of nanostructure.Be used to be satisfied with the needs of hot-spraying techniquess such as plasma spraying, flame plating, electric arc spraying.Its application content is referring to " yttrium of nanostructure is stablized wrong agglomerate type powder of oxidation and production method thereof ", and publication number is CN1587062A.
The old generation honor of contriver, Jiao Xiuling etc. have applied for the preparation method of nanometer zirconium oxide for thermal barrier coating, utilize zirconium oxychloride, yttrium oxide or chlorination to recall for raw material and make mixed solution, in solution, add ammoniacal liquor then, after washing disperses, carry out hydro-thermal reaction in the reactor of packing into and make the stable or partially stabilized cubic phase ZrO of yttrium
2Nano-powder separates, drying or granulation then, or with aluminum oxide nano-powder is carried out carrying out drying or granulation after the surface coats, and heat-treats at last, makes the nanometer zirconium oxide that can be used as heat barrier coat material.Its application content is referring to " preparation method of nanometer zirconium oxide for thermal barrier coating ", and publication number is CN1757605A.
Foregoing invention needs azeotropic distn dehydration, colloidal mill or hydrothermal treatment consists technology, prepares last the reunion again of nano level zirconia powder and granulates, and preparation technology's long flow path needs complexity or high-tension apparatus etc., and output is restricted.
Zirconium oxychloride (ZrOCl
28H
2O) be the basic raw material for chemical industry of the various zirconium products of present industrial production, when producing nano zircite and containing Zirconium oxide, generally adopt in zirconium oxychloride aqueous solution to add the preparation method that ammoniacal liquor is made precipitation agent, at first the zirconium hydroxide precipitate of preparation different moisture content or comprise the precipitation mixture of various ingredients under the condition of pH9～10.Because difficult washing of precipitation mixture and filtration wherein contain impurity such as a large amount of chlorions, ammonium radical ion, are difficult to washing and remove.And with these zirconium hydroxide precipitate (or hydrous zirconium oxide) when preparing nano zirconium oxide powder as precursor, because thermal treatment temp can not too high (being generally less than 900 ℃), otherwise macrobead will be grown up or sinter into to nanometer powder, change the characteristic of nanometer powder.But in order to guarantee to obtain nanometer powder, when handling precursor under this low temperature, the difficult volatilization of chlorion wherein, ammonium radical ion, especially chlorion eliminates, and has had a strong impact on the quality of products such as nano zircite.
Zirconium carbonate (ZrOCO
3NH
2O) be the intermediate raw material of preparation zirconium compounds, it can make water-resisting agent, fire retardant, is used for fiber treatment and paper surface auxiliary agent, is the raw material of industries such as weaving, papermaking, coating.Zirconium carbonate is formed complicated, and the composition of resultant is unfixing yet under the different condition, and zirconium carbonate has following several form: Zr
2O
3(OH)
2CO
3NH
2O (or ZrOCO
3ZrO (OH)
2XH
2O), Zr (OH)
2CO
3NH
2O, ZrO
2CO
3NH
2O, ZrOCO
3NH
2O, the difference of forming according to its structure can be described as zirconyl carbonate again, and zirconium carbonate that refers generally to and zirconyl carbonate are the mixture of above-mentioned various ways.The nano-calcium carbonate zirconium can with other nano metal compound, after the spray-dried granulation, in electric furnace, through 350～400 ℃ of following thermal treatments after 3～5 hours, be warming up to 700～850 ℃ and be incubated 12～16 hours and heat-treat, obtain the nano zircite ZrO of doping different substances and amount
2Or the nano rare earth zirconate RE of pyrochlore-type crystalline structure
2Zr
2O
7Agglomerate type powder, the zirconium compounds powder inside of these nanostructures has vesicular structure, is adapted to heat barrier coat material.
The production method of industrial carbonic acid zirconium mainly contains following several.The one, in zirconic hydrochloric acid soln, add carbonate, generate (common) zirconium carbonate and precipitate, then itself and bicarbonate of ammonia reaction are generated zirconium carbonate ammonium, in zirconium carbonate ammonium solution, add the dispersion agent post-heating and decompose the ultra-fine or nanometer high reactivity carbonic acid zirconium of generation.Use the zirconium carbonate of this explained hereafter, the product activity is good, and foreign matter content is low, but technical process is long, and control is complicated, and is tighter to the equipment performance requirement, so production cost is higher.The 2nd, adopt substep liquid-phase precipitation technology, i.e. zirconium oxychloride → zirconium basic sulphate → filtering and washing → zirconium carbonate → filtering and washing.Earlier zirconium oxychloride is made solution, import a certain amount of sulfuric acid (or vitriol) and catalyzer then in proportion, add back control stirring velocity, system is warming up to certain temperature, keeps system temperature after for some time, sampling its morphological structure of microscopic, back up to standard stopped reaction, with the deionized water wash precipitation, zirconium basic sulphate and carbonate after will washing react at normal temperatures and pressures again, can generate zirconium carbonate.The 3rd, adopt one-step technology production, manufacturer's employing zirconyl chloride solution and metabisulfite solution reaction generation sodium zirconium sulfate compound as domestic zirconium carbonate make zirconium carbonate with reaction of sodium bicarbonate then.
Practical situation at production process, utilize the zirconium carbonate filterableness relatively better to reach impurity easily by the characteristic of flush away, adopting cheap zirconium oxychloride is raw material, after being converted into zirconium carbonate precursors such as (or zirconyl carbonates), again through thermal treatment, nanometer that availability is good or superfine zirconia product.Also can utilize these precursors to mix easily with other material simultaneously, prepare various zirconic nanometers or super-refinement compound, required production unit is simple, the technology condition gentleness.
[summary of the invention]: the present invention seeks to solve the prior art above shortcomings, a kind of Conglobation type nano zirconium-containing series thermal barrier coating preparation methods is provided.
The concrete preparation process of the inventive method is as follows:
The first, adopting cheap zirconium oxychloride is raw material, at first prepares the mixture of the compound of zirconium carbonate or zirconyl carbonate and other element, and concrete grammar is as follows:
Method one, with zirconium oxychloride ZrOCl
28H
2O is made into the aqueous solution of 0.5～2.5mol/L, is that (the industrial goods volatile salt is the two a double salt of bicarbonate of ammonia and ammonium carbamate to precipitation agent with volatile salt or bicarbonate of ammonia; Industrial in addition normal custom is called volatile salt with bicarbonate of ammonia, be called for short the carbon ammonium), be made into the aqueous solution that concentration is 0.5～3mol/L, volatile salt or ammonium bicarbonate aqueous solution are joined in the zirconium oxychloride aqueous solution by 100～105% of requirement, by zirconium carbonate or the zirconyl carbonate throw out that sedimentary method obtains to be easy to wash, chloride ion content is low, through washing, filtration, till detecting less than chlorion, size mixing gained zirconium carbonate or zirconyl carbonate throw out water standby with Silver Nitrate; Mix by total content 0.1～21% with oxide compound, oxyhydroxide, carbonate or the jelly of alkaline-earth metal, rare earth metal or aluminium or in the aluminium carbonate ammonium one or more again, perhaps,
Method two, with zirconium oxychloride ZrOCl
28H
2O is made into the aqueous solution that concentration is 0.5～2.5mol/L, in zirconium oxychloride aqueous solution in the water soluble salt of needed alkaline-earth metal of adding or rare earth metal one or more, add additives polyethylene glycol 20～50ml by every liter of zirconium oxychloride aqueous solution again, at last with concentration be the volatile salt of 0.5～3mol/L or ammonium bicarbonate aqueous solution by requirement 100～105% with above-mentioned mixing solutions reaction, after thorough washing filters, obtain the mixture of zirconium carbonate or zirconyl carbonate and alkaline-earth metal, rare earth metal carbonate sediment; Perhaps,
Method three, with zirconium oxychloride ZrOCl
28H
2O is made into the aqueous solution that concentration is 0.5～2.5mol/L, at zirconium oxychloride ZrOCl
28H
2Press 100～105% of requirement in the O aqueous solution and add volatile salt or bicarbonate of ammonia, generate zirconium carbonate or zirconyl carbonate throw out, through washing, filtration, till detecting less than chlorion with Silver Nitrate, gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing standby; And then add excessive bicarbonate of ammonia and zirconium carbonate or zirconyl carbonate throw out are transformed generate zirconium carbonate ammonium, in zirconium carbonate ammonium solution, add additives polyethylene glycol, be heated to 85～95 ℃ and decompose generation zirconium carbonate or zirconyl carbonate, the sedimentary weight ratio of additives polyethylene glycol and zirconium carbonate or zirconyl carbonate is 40～60: 1000, and the zirconium carbonate throw out after the filtration is sized mixing with deionized water; Again with oxide compound, oxyhydroxide, the carbonate of alkaline-earth metal, rare earth metal or aluminium, or one or more mixing in the aluminium carbonate ammonium;
The second, the above-mentioned mixture that makes was carried out stirring ball-milling 30～60 minutes;
Three, spray-drying process; Adopt centrifugal or press spray drying plant, spray-dired heating temperature of inlet air is 180～300 ℃, and temperature out is 105～220 ℃; In the spraying drying jar, collect powder, after screening, send thermal treatment, fine-graded dried powder then utilizes the cyclonic separation dust-precipitator and the bagroom that link to each other with the spraying drying jar to collect, and after returning next process and zirconium carbonate or zirconyl carbonate and mixing, the ball milling batching is carried out spray-drying process once more.The primary particle of agglomerate type powder is a nanostructure, and the coacervate granularity then is a micron granularity, and the main body size range is 10～100 μ m, is shaped as sphere or class sphere.
Four, thermal treatment; Conglobation type sphere or class spherical powder through 350～400 ℃ of following thermal treatments after 3～5 hours, are warming up to 700～850 ℃ and be incubated 12～16 hours in electric furnace, obtain the nano zircite ZrO of doping different substances
2Or the nano rare earth zirconate RE of pyrochlore-type crystalline structure
2Zr
2O
7Agglomerate type powder, wherein nano rare earth zirconate RE
2Zr
2O
7Only contain rare earth, and alkali-free soil and aluminium element, RE: the Zr mol ratio is controlled at 1～1.05: in 1 scope, the zirconium compounds powder inside of these nanostructures has vesicular structure, is adapted to heat barrier coat material.
Above-mentioned nano zircite ZrO
2In adulterated alkaline-earth metal, rare earth metal and light metal element be calcium Ca, magnesium Mg, yttrium Y, lanthanum La, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, ytterbium Yb, and among the aluminium Al one or more.
At nano rare earth zirconate RE
2Zr
2O
7In the agglomerate type powder, RE is one or more among yttrium Y, lanthanum La, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er or the ytterbium Yb.
When mixing aluminium element, pseudo-boehmite, boehmite water to be sized mixing, the aqueous nitric acid that dropwise added 1: 1 is regulated pH value of slurry, till some one-tenth colloid of pH value 1.5～4; Or be raw material with the aluminium carbonate ammonium, directly mixing with zirconium carbonate or zirconyl carbonate, aluminum content counts 0.5～5% by aluminum oxide.
Advantage of the present invention and positively effect:
The present invention adopts cheap zirconium oxychloride (ZrOCl
28H
2O) and volatile salt or bicarbonate of ammonia be raw material, zirconium carbonate or zirconyl carbonate that acquisition is easy to wash, chloride ion content is low, mix with in gluey oxyhydroxide, carbonate deposition or other compound of alkaline-earth metal, rare earth metal, aluminium one or more as required again, after stirring ball-milling, spray-drying process, thermal treatment process, obtain Conglobation type nanostructured zirconium compounds powder-product, as the nano zircite ZrO of doping different substances
2Or the nano rare earth zirconate RE of pyrochlore-type crystalline structure
2Zr
2O
7These Conglobation types contain nanometer zirconium compounds powder also can further be handled through plasma ball-type densification process, to satisfy the different service requirementss of material.The product of this preparation method preparation can satisfy simultaneously in the agglomerate type powder that chloride ion content is low, primary particle is that nano particle size, composition are easy to requirements such as regulation and control, has realized containing low-cost gentle preparation of zirconium nano-oxide.
It is extensive that the present invention also has raw material sources, and preparation method's adaptability is strong, flow process short, is easy to mass-producing, and production cost is low, the characteristics of good product quality.By the decomposition of control carbonate, CO
2Stay tiny hole behind the gas evolution, help obtaining the porous Conglobation type and contain zirconium Nano compound particle powder, be particularly suitable for the preparation material of thermal barrier coating.
[embodiment]:
Embodiment 1:
The throw out hybrid system prepares the doped nano zirconia reunion powder.Take by weighing zirconium oxychloride (ZrOCl
28H
2O) 520g is dissolved in being made in the distilled water of 2 liters of volumes and contains the solution that zirconium concentration is about 0.75mol/L, and heating makes the temperature of solution reach 80～85 ℃; In addition bicarbonate of ammonia 240g is dissolved in 2 liters of distilled water, be made into the solution (or volatile salt 150gl adds a about 1.5mol/L sal volatile of preparation in one liter of distilled water) that contains the hydrogen-carbonate ammonium concentration and be about 1.5mol/L, be heated to 40～50 ℃, it is added drop-wise in the zirconium oxychloride aqueous solution, constantly stir, generate white zirconium carbonate or zirconyl carbonate throw out, and adding 15ml1: 1 ammoniacal liquor (concentration about 12.5%), through centrifuging, pulp washing, repeat repeatedly, till detecting less than chlorion with Silver Nitrate, gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing standby.
Take by weighing yttrium oxide 13.5g, wetting with 80ml distilled water in beaker, heated and stirred to 60 ℃, add 12% rare nitric acid 115ml dissolving, after having dissolved, drip 1: 1 ammoniacal liquor 60ml, constantly stirring precipitates solution fully, static 12 hours, with the supernatant liquor sucking-off, with the centrifuging of throw out yttrium hydroxide, and once with the 200ml distilled water wash, after the centrifuging yttrium hydroxide is added in above-mentioned obtained zirconium carbonate or the zirconyl carbonate throw out water slurry,, send spray-drying process through stirring ball-milling 30～60 minutes.Adopt centrifugal spray drying device, spray-dired heating temperature of inlet air is 260～280 ℃, and temperature out is 110～125 ℃; In the spraying drying jar, collect powder, after screening, send thermal treatment, fine-graded dried powder then utilizes the cyclonic separation dust-precipitator and the bagroom that link to each other with the spraying drying jar to collect, return mix with the next batch material after, the ball milling batching, carry out spray-drying process once more, the heating temperature of inlet air is 280～290 ℃, and temperature out is 110～120 ℃.The granulation material through 350～400 ℃ of following thermal treatments after 3～5 hours, is warming up to 830 ℃ and be incubated 12～16 hours in electric furnace, obtain the nano zircite spherical powder of Conglobation type doped yttrium oxide 7%.Through scanning electron microscope analysis, the primary particle of agglomerate type powder is a nanostructure, about 30～80nm, the coacervate granularity then is a micron granularity, 90% size range is 10～100 μ m, is shaped as sphere or class sphere, becomes the product that satisfies different spraying coating process after the screening.
With above-mentioned identical method, with alkaline earth metals calcium Ca or magnesium Mg, rare earth lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or one or more oxide compounds among the ytterbium Yb, oxyhydroxide, carbonate, ratio in incorporation, measure 13.5g by oxycompound, replace with yttrium oxide for mixing the yttrium raw material, and with preparing the identical method of yttrium hydroxide, use nitric acid dissolve, or directly be mixed with the aqueous solution with its nitrate, add ammoniacal liquor, a kind of aqueous solution in volatile salt or the bicarbonate of ammonia, obtain alkaline-earth metal, or the oxyhydroxide of rare earth metal, carbonate deposition, adding above-mentioned obtained water withers in slurry back zirconium carbonate or the zirconyl carbonate throw out water slurry, through stirring ball-milling 30～60 minutes, send spray-drying process, the heating temperature of inlet air is 180～300 ℃, temperature out is 105～220 ℃, the granulation material in electric furnace through 350～400 ℃ of following thermal treatments after 3～5 hours, be warming up to 830 ℃ and be incubated 12～16 hours, obtain Conglobation type a kind of Different Alkali earth metals that mixes, the rare earth metal amount is 7% nano zircite spherical powder, perhaps alkaline earth metals calcium Ca or magnesium Mg, rare earth lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or among the ytterbium Yb two or more, mix as raw material by amounting to into oxide compound gross weight sum 13.5g, with above-mentioned identical method, all can obtain adulterated alkaline-earth metal calcium Ca or magnesium Mg at last, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or two or more the nano zircite spherical powder of ytterbium Yb.Prepared doped nano zirconia spherical powder, mix a kind of or simultaneously the amount in multiple alkaline-earth metal and the rare earth metal account for the nano zircite reunion powder weight ratio as required setting range be 0.1～21%.
When mixing aluminium element, take by weighing pseudo-boehmite 3.8g, pour in the beaker, add 60ml distilled water, stirring and evenly mixing, pH value to 1.5～4 with 1: 1 salpeter solution adjusting water, become jelly, pour into again in above-mentioned prepared yttrium hydroxide and zirconium carbonate or the sedimentary water slurry of zirconyl carbonate, by above-mentioned identical processing parameter, after stirring ball-milling, spray-drying process, thermal treatment, obtain to mix the nano zircite agglomerate type powder that aluminium is about 1.2%, mix yttrium oxide about 7%.Above-mentioned yttrium hydroxide also can use the same method, and is replaced or common the doping nano zircite reunion powder of one or more alkaline-earth metal of preparation doping, thulium by other alkaline-earth metal, rare earth compound.Pseudo-boehmite can use boehmite, aluminium hydroxide or aluminium carbonate ammonium raw material to replace, aluminum feedstock is mixed in preparation, zirconium carbonate after sizing mixing with water then or one or more precipitation mixture remix in zirconyl carbonate and above-mentioned alkaline-earth metal or the rare earth metal, after identical stirring ball-milling, spray-drying process, thermal treatment process, the nano zircite reunion powder of one or more in preparation adulterated alkaline-earth metal, rare earth metal and the aluminium element.
Embodiment 2:
The throw out hybrid system prepares dopen Nano RE
2Zr
2O
7Reunion powder.Take by weighing zirconium oxychloride (ZrOCl
28H
2O) 520g is dissolved in being made in the distilled water of 2 liters of volumes and contains the solution that zirconium concentration is about 0.75mol/L, and heating makes the temperature of solution reach 80～85 ℃; In addition bicarbonate of ammonia 240g is dissolved in 2 liters of distilled water, be made into the solution (or volatile salt 150gl adds a about 1.5mol/L sal volatile of preparation in one liter of distilled water) that contains the hydrogen-carbonate ammonium concentration and be about 1.5mol/L, be heated to 40～50 ℃, it is added drop-wise in the zirconium oxychloride aqueous solution, constantly stir, generate white zirconium carbonate or zirconyl carbonate throw out, and adding 15ml1: 1 ammoniacal liquor (concentration about 12.5%), through centrifuging, pulp washing, repeat repeatedly, till detecting less than chlorion with Silver Nitrate, gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing standby.
Take by weighing lanthanum trioxide 239g, wetting with 1000ml distilled water in beaker, heated and stirred to 65 ℃, add 12% rare nitric acid 2490ml dissolving, after having dissolved, till constantly stirring and drip when ammoniacal liquor did not extremely precipitate in 1: 1, solution is precipitated fully, static 18 hours, with the supernatant sucking-off, with the centrifuging of throw out lanthanum hydroxide, and use the distilled water wash secondary, after the centrifuging lanthanum hydroxide is added in above-mentioned obtained zirconium carbonate or the zirconyl carbonate throw out water slurry, through stirring ball-milling 120～180 minutes, send spray-drying process, the heating temperature of inlet air is 180～300 ℃, and temperature out is 105～220 ℃.In electric furnace, through 350～400 ℃ of following thermal treatments after 3～5 hours, be warming up to 800 ℃ and be incubated 12～16 hours, obtain Conglobation type La
2Zr
2O
7Nano zircite spherical powder, wherein La: Zr (mol ratio) is controlled in 1～1.05: 1 scope.
When replacing lanthanum trioxide with cerous carbonate 332g, Neodymium trioxide 243g, yttrium oxide 163g, Samarium trioxide 252g, europium sesquioxide 254g, gadolinium sesquioxide 262g, dysprosium oxide 269g, Erbium trioxide 276g or ytterbium oxide 285g respectively, with above-mentioned identical method, prepare the RE of other rare earth element
2Zr
2O
7The nano zircite spherical powder becomes product, wherein RE after the screening: Zr (mol ratio) is controlled in 1～1.05: 1 scope.Used raw material can also be rare-earth hydroxide and rare earth carbonate, and in RE: Zr (mol ratio) is 1～1.05: 1 ratio, can mix among lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er or the ytterbium Yb two or more simultaneously.As in La: Y: Ce=7: ratio was mixed lanthanum La, yttrium Y, three kinds of rare earth oxides of cerium Ce simultaneously in 2: 1, then mix with lanthanum trioxide 167.7g, yttrium oxide 32.6g, cerous carbonate 33.2g, replace lanthanum oxide material,, obtain Conglobation type La with above-mentioned identical method
0.7Y
0.2Ce
0.1Zr
2O
7The nano zircite spherical powder mixes oxide compound.RE
2Zr
2O
7In RE do not comprise alkaline earth metals calcium Ca, magnesium Mg and aluminium Al.
Embodiment 3
Prepared by co-precipitation doped nano zirconia reunion powder.Take by weighing zirconium oxychloride (ZrOCl
28H
2O) 520g is dissolved in being made in the distilled water of 2 liters of volumes and contains the solution that zirconium concentration is about 0.75mol/L, and heating makes the temperature of solution reach 60～65 ℃; Take by weighing lanthanum trioxide 239g, wetting with 1000ml distilled water in beaker, heated and stirred to 65 ℃, add 12% rare nitric acid 2490ml dissolving, after having dissolved, till constantly stirring and drip when ammoniacal liquor did not extremely precipitate in 1: 1, solution is precipitated fully, static 18 hours, with the supernatant sucking-off, with the centrifuging of throw out lanthanum hydroxide, and use the distilled water wash secondary, after the centrifuging lanthanum hydroxide is added in above-mentioned obtained zirconium carbonate or the zirconyl carbonate throw out water slurry, through stirring ball-milling 120～180 minutes, send spray-drying process, the heating temperature of inlet air is 260～280 ℃, and temperature out is 130～140 ℃, the granulation material in electric furnace through 350～400 ℃ of following thermal treatments after 3～5 hours, be warming up to 780 ℃ and be incubated 12～16 hours, obtain Conglobation type La
2Zr
2O
7Nano zircite spherical powder, wherein La: Zr (mol ratio) is controlled in 1～1.05: 1 scope.
After dripping pH value to 1～1.5 of 1: 1 ammoniacal liquor adjustment yttrium nitrate solution, join in the zirconium oxychloride aqueous solution, heating makes the temperature of solution reach 60～80 ℃, add 50ml polyoxyethylene glycol (PEG) again, stir, other takes by weighing bicarbonate of ammonia 240g and is dissolved in 2 liters of distilled water, be made into the solution (or volatile salt 150gl adds a about 1.5mol/L sal volatile of preparation in one liter of distilled water) that contains the hydrogen-carbonate ammonium concentration and be about 1.5mol/L, be heated to 40～50 ℃, volatile salt (or bicarbonate of ammonia) solution is poured in the mixing solutions of zirconium oxychloride and Yttrium trinitrate fast, generate zirconium carbonate or zirconyl carbonate and yttrium hydroxide white precipitate mixture, static 24 hours, with the supernatant liquor sucking-off, the bottom throw out is after thorough washing filters, filter residue changes in the ball mill, adding water sizes mixing, stirring ball-milling 30～60 minutes, send spray-drying process, the heating temperature of inlet air is 230～260 ℃, temperature out is 130～140 ℃, and the granulation material earlier through 350～400 ℃ of following thermal treatments 3～5 hours, heats up 800 ℃ and be incubated 12～16 hours in electric furnace, obtain Conglobation type and mix the yttrium nano zircite, become product after the screening.
Metallic yttrium element in the above method also can be replaced with other metallic element, as alkaline-earth metal, or the calcium Ca in the rare earth metal, magnesium Mg, or lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, one or more oxide compounds among the ytterbium Yb, oxyhydroxide or carbonate, by amounting to into oxide compound 13.5g weight metering, through nitric acid dissolve or directly use its nitrate, drip 1: 1 ammoniacal liquor and adjust the pH value of yttrium nitrate solution to l～1.5, join in the zirconium oxychloride aqueous solution then, handle with above-mentioned identical method, obtain the above-mentioned alkaline-earth metal that mixes, a kind of in the rare earth metal or the nano zircite reunion powder of multiple alkaline-earth metal and rare earth metal simultaneously, mix a kind of or simultaneously the amount in multiple alkaline-earth metal and the rare earth metal account for the nano zircite reunion powder weight ratio as required setting range be 0.1～21%.
When mixing aluminium element, take by weighing aluminium hydroxide 4.9g, pour in the beaker, add 80ml distilled water, stirring and evenly mixing, dripping 12% diluted nitric acid aqueous solution to aluminium hydroxide dissolves fully, form aluminum nitrate solution, use 1: 1 dilute ammonia solution to regulate about the pH value to 1.5 of aluminum nitrate solution again, pour into again in above-mentioned prepared yttrium hydroxide and zirconium carbonate or the sedimentary water slurry of zirconyl carbonate, by above-mentioned identical processing parameter, through stirring ball-milling, spray-drying process, after the thermal treatment, obtain to mix aluminium about 1.2%, mix the nano zircite agglomerate type powder of yttrium oxide about 7%.Above-mentioned yttrium hydroxide also can use the same method, and is replaced or common the doping nano zircite reunion powder of one or more alkaline-earth metal of preparation doping, thulium by other alkaline-earth metal, rare earth compound.Aluminium hydroxide can use pseudo-boehmite, boehmite, aluminium hydroxide or aluminium carbonate ammonium raw material to replace, aluminum feedstock is mixed in preparation, zirconium carbonate after sizing mixing with water then or one or more precipitation mixture remix in zirconyl carbonate and above-mentioned alkaline-earth metal or the rare earth metal, after identical stirring ball-milling, spray-drying process, thermal treatment process, the nano zircite reunion powder of one or more in preparation adulterated alkaline-earth metal, rare earth metal and the aluminium element.
Embodiment 4
Coprecipitation method prepares nanometer RE
2Zr
2O
7Reunion powder.Take by weighing zirconium oxychloride (ZrOCl
28H
2O) 520g is made in the distilled water of water-soluble 2 liters of volumes and contains the solution that zirconium concentration is about 0.75mol/L, and heating makes the temperature of solution reach 80～85 ℃; Take by weighing lanthanum trioxide 239g, wetting with 1000ml distilled water in beaker, add 12% rare nitric acid 2490ml dissolving, after heated and stirred to 65 ℃ has been dissolved, drip 1: 1 ammoniacal liquor to pH value of solution and be about about 1.2, form lanthanum nitrate aqueous solution, mix with zirconium oxychloride aqueous solution.In addition bicarbonate of ammonia 480g is dissolved in 4 liters of distilled water, be made into the solution (or volatile salt 300gl adds a about 1.5mol/L sal volatile of preparation in 2 liters of distilled water) that contains the hydrogen-carbonate ammonium concentration and be about 1.5mol/L, be heated to 40～50 ℃, it is added drop-wise in the zirconium oxychloride and the mixed aqueous solution of lanthanum nitrate, constantly stir and make precipitation evenly, generate zirconium carbonate or zirconyl carbonate and lanthanum hydroxide white precipitate mixture, static 24 hours, with the supernatant liquor sucking-off, the bottom throw out is after thorough washing filters, and filter residue changes in the ball mill, adding water sizes mixing, stirring ball-milling 30～60 minutes send spray-drying process, and the heating temperature of inlet air is 210～250 ℃, temperature out is 105～115 ℃, the granulation material earlier through 350～400 ℃ of following thermal treatments 5 hours, is warming up to 780 ℃ and be incubated 14 hours in electric furnace, obtain Conglobation type nanometer La
2Zr
2O
7Reunion powder.Through scanning electron microscope analysis, the primary particle of agglomerate type powder is a nanostructure, about 35～75nm, and the coacervate granularity then is a micron granularity, 95% size range is 10～100 μ m, becomes product after the screening.Wherein La: Zr (mol ratio) is controlled in 1～1.05: 1 scope.
When replacing lanthanum trioxide with cerous carbonate 332g, Neodymium trioxide 243g, yttrium oxide 163g, Samarium trioxide 252g, europium sesquioxide 254g, gadolinium sesquioxide 262g, dysprosium oxide 269g, Erbium trioxide 276g or ytterbium oxide 285g respectively, with above-mentioned identical method, prepare the RE of other rare earth element
2Zr
2O
7The nano zircite spherical powder becomes product, wherein RE after the screening: Zr (mol ratio) is controlled in 1～1.05: 1 scope.Used raw material can also be rare-earth hydroxide and rare earth carbonate, and in RE: Zr (mol ratio) is 1～1.05: 1 ratio, can mix among lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er or the ytterbium Yb two or more simultaneously.As in La: Gd: Nd=80: ratio was mixed lanthanum La, gadolinium Gd, three kinds of rare earth oxides of neodymium Gd simultaneously in 15: 5, then mix with lanthanum trioxide 191.7g, gadolinium sesquioxide 39.3g, Neodymium trioxide 12.2g, replace lanthanum oxide material, with above-mentioned identical method, obtain to contain simultaneously the Conglobation type nanometer La of multiple rare earth element
0.8Gd
0.15Nd
0.05Zr
2O
7Spherical powder.RE
2Zr
2O
7In RE do not comprise alkaline earth metals calcium Ca, magnesium Mg and aluminium Al.
Embodiment 5
Zirconium carbonate ammonium thermal degradation legal system is equipped with the zirconium carbonate throw out, and then the doped nano zirconia reunion powder.Take by weighing zirconium oxychloride (ZrOCl
28H
2O) 520g is made in the distilled water of water-soluble 2 liters of volumes and contains the solution that zirconium concentration is about 0.75mol/L, and heating makes the temperature of solution reach 75～80 ℃.In addition bicarbonate of ammonia 240g is dissolved in 2 liters of distilled water, be made into the solution (or volatile salt 150gl adds a about 1.5mol/L sal volatile of preparation in one liter of distilled water) that contains the hydrogen-carbonate ammonium concentration and be about 1.5mol/L, be heated to 40～50 ℃, it is added drop-wise in the zirconium oxychloride aqueous solution, constantly stir, generate white zirconium carbonate or zirconyl carbonate throw out, and add H and go into 15ml1: 1 ammoniacal liquor (concentration about 12.5%), through centrifuging, pulp washing, repeat repeatedly, till detecting less than chlorion with Silver Nitrate, gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing standby.After gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing, adding concentration is the ammonium bicarbonate soln of 1.5mol/L, and the continuous solid particulate solution that makes in the water slurry that stirs, reaction generates zirconium carbonate ammonium solution, in zirconium carbonate ammonium solution, add additives polyethylene glycol (in the ratio of 1000g zirconium carbonate or zirconyl carbonate throw out add-on 50g), be heated to 95 ℃ and decompose the generation zirconium carbonate, after static 24 hours, with the supernatant sucking-off, centrifuging bottom settlings thing, and use 75～80 ℃ distilled water wash again, filter through repeating secondary centrifuging, after the washing throw out, with distilled water with zirconium carbonate throw out size mixing (solid content remains on 15～25%).
Take by weighing gadolinium sesquioxide 13.5g, wetting with 80ml distilled water in beaker, heated and stirred to 60 ℃, add 12% rare nitric acid 85ml dissolving, after having dissolved, drip 1: 1 ammoniacal liquor 40ml, constantly stirring precipitates solution fully, static 16 hours, with the supernatant liquor sucking-off, with the centrifuging of throw out gadolinium hydroxide, and once with the 200ml distilled water wash, after the centrifuging gadolinium hydroxide added above-mentioned obtained solid content and be about 22% transform in the zirconium carbonate water slurry that makes,, send spray-drying process through stirring ball-milling 50 minutes by zirconium carbonate ammonium.Adopt the press spray drying plant, spray-dired heating temperature of inlet air is 280～300 ℃, and temperature out is 105～115 ℃; In the spraying drying jar, collect powder, send thermal treatment after screening, fine-graded dried powder then utilizes the cyclonic separation dust-precipitator that links to each other with the spraying drying jar and bagroom to collect, return with the next batch material mixed after, the ball milling batching is carried out spray-drying process once more.The granulation material through 350～400 ℃ of following thermal treatments after 3 hours, is warming up to 800～820 ℃ and be incubated 15 hours in electric furnace, obtain the nano zircite spherical powder of Conglobation type doping gadolinium sesquioxide 7%.Through scanning electron microscope analysis, the primary particle of agglomerate type powder is a nanostructure, about 40～70nm, the coacervate granularity then is a micron granularity, 92% size range is 10～100 μ m, is shaped as sphere or class sphere, becomes the product that satisfies different spraying coating process after the screening.
With above-mentioned identical method, with alkaline earth metals calcium Ca or magnesium Mg, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or one or more oxide compounds among the ytterbium Yb, oxyhydroxide, carbonate, ratio in incorporation, measure 13.5g by oxycompound, replace with yttrium oxide for mixing the yttrium raw material, and with preparing the identical method of yttrium hydroxide, use nitric acid dissolve, or directly be mixed with the aqueous solution with its nitrate, add ammoniacal liquor, a kind of aqueous solution in volatile salt or the bicarbonate of ammonia, obtain alkaline-earth metal, or the oxyhydroxide of rare earth metal, carbonate deposition, adding above-mentioned obtained water sizes mixing in back zirconium carbonate or the zirconyl carbonate throw out water slurry, through stirring ball-milling 30～60 minutes, send spray-drying process, the heating temperature of inlet air is 240～280 ℃, temperature out is 130～140 ℃, the granulation material in electric furnace through 350～400 ℃ of following thermal treatments after 3～5 hours, be warming up to 800～820 ℃ and be incubated 12～16 hours, obtain Conglobation type a kind of different alkali oxide earth metals that mixes, the rare earth metal amount is 7% nano zircite spherical powder, perhaps alkaline earth metals calcium Ca or magnesium Mg, rare earth lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or two or more of ytterbium Yb, mix as raw material by amounting to into oxide compound gross weight sum 13.5g, with above-mentioned identical method, all can obtain adulterated alkaline-earth metal calcium Ca or magnesium Mg at last, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or two or more the nano zircite spherical powder of ytterbium Yb.Prepared doped nano zirconia spherical powder, mix a kind of or simultaneously the amount in multiple alkaline-earth metal and the rare earth metal account for the nano zircite reunion powder weight ratio as required setting range be 0.1～21%.Through scanning electron microscope analysis, the primary particle of agglomerate type powder is a nanostructure, about 30～80nm, the coacervate granularity then is a micron granularity, 91% size range is 10～100 μ m, is shaped as sphere or class sphere, becomes the product that satisfies different spraying coating process after the screening.
When mixing aluminium element, take by weighing pseudo-boehmite 3.8g, pour in the beaker, add 60ml distilled water, stirring and evenly mixing, pH value to 1.5～4 with 1: 1 salpeter solution adjusting water, become jelly, pour into again in above-mentioned prepared gadolinium hydroxide and zirconium carbonate or the sedimentary water slurry of zirconyl carbonate, by above-mentioned identical processing parameter, after stirring ball-milling, spray-drying process, thermal treatment, obtain to mix the nano zircite agglomerate type powder that aluminium is about 1.2%, mix gadolinium sesquioxide about 7%.Above-mentioned gadolinium hydroxide is also available to be replaced or common the doping nano zircite reunion powder of one or more alkaline-earth metal of preparation doping, thulium by other alkaline-earth metal, rare earth compound.Pseudo-boehmite can use boehmite, aluminium hydroxide or aluminium carbonate ammonium raw material to replace, aluminum feedstock is mixed in preparation, zirconium carbonate after sizing mixing with water then or one or more precipitation mixture remix in zirconyl carbonate and above-mentioned alkaline-earth metal or the rare earth metal, after identical stirring ball-milling, spray-drying process, thermal treatment process, the nano zircite reunion powder of one or more in preparation adulterated alkaline-earth metal, rare earth metal and the aluminium element.
Embodiment 6
Zirconium carbonate ammonium thermal degradation legal system is equipped with the zirconium carbonate throw out, and then the doped nano zirconia reunion powder.Take by weighing zirconium oxychloride (ZrOCl
28H
2O) 520g is made in the distilled water of water-soluble 2 liters of volumes and contains the solution that zirconium concentration is about 0.75mol/L, and heating makes the temperature of solution reach 75～80 ℃.In addition bicarbonate of ammonia 240g is dissolved in 2 liters of distilled water, be made into the solution (or volatile salt 150gl adds a about 1.5mol/L sal volatile of preparation in one liter of distilled water) that contains the hydrogen-carbonate ammonium concentration and be about 1.5mol/L, be heated to 40～50 ℃, it is added drop-wise in the zirconium oxychloride aqueous solution, constantly stir, generate white zirconium carbonate or zirconyl carbonate throw out, and adding 15ml1: 1 ammoniacal liquor (concentration about 12.5%), through centrifuging, pulp washing, repeat repeatedly, till detecting less than chlorion with Silver Nitrate, gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing standby.After gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing, adding concentration is the ammonium bicarbonate soln of 1.5mol/L, and the continuous solid particulate solution that makes in the water slurry that stirs, reaction generates zirconium carbonate ammonium solution, in zirconium carbonate ammonium solution, add additives polyethylene glycol (in the ratio of 1000g zirconium carbonate or zirconyl carbonate throw out add-on 50g), be heated to 95 ℃ and decompose the generation zirconium carbonate, after static 24 hours, with the supernatant sucking-off, centrifuging bottom settlings thing, and use 75～80 ℃ distilled water wash again, filter through repeating secondary centrifuging, after the washing throw out, with distilled water with zirconium carbonate throw out size mixing (solid content remains on 15～25%).
Take by weighing Samarium trioxide 252g, wetting with 1000ml distilled water in beaker, heated and stirred to 65 ℃, add 12% rare nitric acid 2490ml dissolving, after having dissolved, till constantly stirring and drip when ammoniacal liquor did not extremely precipitate in 1: 1, solution is precipitated fully, static 18 hours, with the supernatant sucking-off, with the centrifuging of throw out samaric hydroxide, and use the distilled water wash secondary, after the centrifuging samaric hydroxide is added in above-mentioned obtained zirconium carbonate or the zirconyl carbonate throw out water slurry, through stirring ball-milling 120～180 minutes, send spray-drying process, the heating temperature of inlet air is 220～260 ℃, and temperature out is 110～120 ℃, the granulation material in electric furnace through 350～400 ℃ of following thermal treatments after 3～5 hours, be warming up to 800 ℃ and be incubated 12～16 hours, obtain Conglobation type Sm
2Zr
2O
7Nano zircite spherical powder, wherein Sm: Zr (mol ratio) is controlled in 1～1.05: 1 scope.
When replacing Samarium trioxide with cerous carbonate 332g, Neodymium trioxide 243g, yttrium oxide 163g, lanthanum trioxide 239g, europium sesquioxide 254g, gadolinium sesquioxide 262g, dysprosium oxide 269g, Erbium trioxide 276g or ytterbium oxide 285g respectively, with above-mentioned identical method, prepare the RE of other rare earth element
2Zr
2O
7The nano zircite spherical powder becomes product, wherein RE after the screening: Zr (mol ratio) is controlled in 1～1.05: 1 scope.Used raw material can also be rare-earth hydroxide and rare earth carbonate, and in RE: Zr (mol ratio) is 1～1.05: 1 ratio, can mix among lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er or the ytterbium Yb two or more simultaneously.As in Sm: La: Y=80: ratio was mixed lanthanum La, yttrium Y, three kinds of rare earth oxides of cerium Ce simultaneously in 1: 1, then mixed with Samarium trioxide 202g, lanthanum trioxide 23.9g, yttrium oxide 16.3g, replaced the Samarium trioxide raw material, with above-mentioned identical method, and acquisition Conglobation type Sm
0.8Y
0.1Ce
0.1Zr
2O
7The nano zircite spherical powder mixes oxide compound.Through scanning electron microscope analysis, the primary particle of agglomerate type powder is a nanostructure, about 35～90nm, the coacervate granularity then is a micron granularity, 93% size range is 10～100 μ m, is shaped as sphere or class sphere, becomes the product that satisfies different spraying coating process after the screening.RE
2Zr
2O
7In RE do not comprise alkaline earth metals calcium Ca, magnesium Mg and aluminium Al.
Claims (4)
1. nano zirconium-containing series thermal barrier coating preparation methods is characterized in that this method is through following steps:
The first, adopting cheap zirconium oxychloride is raw material, at first prepares the mixture of the compound of zirconium carbonate or zirconyl carbonate and other element, and concrete grammar is as follows:
Method one, with zirconium oxychloride ZrOCl
28H
2O is made into the aqueous solution that concentration is 0.5～2.5mol/L, with volatile salt or bicarbonate of ammonia is precipitation agent, be made into the aqueous solution that concentration is 0.5～3mol/L, volatile salt or ammonium bicarbonate aqueous solution are joined in the zirconium oxychloride aqueous solution by 100～105% of requirement, by zirconium carbonate or the zirconyl carbonate throw out that sedimentary method obtains to be easy to wash, chloride ion content is low, through washing, filtration, till detecting less than chlorion, size mixing gained zirconium carbonate or zirconyl carbonate throw out water standby with Silver Nitrate; Again with oxide compound, oxyhydroxide, the carbonate of alkaline-earth metal, rare earth metal or aluminium, or in the aluminium carbonate ammonium one or more are pressed total content 0.1～21% and are mixed; Perhaps,
Method two, with zirconium oxychloride ZrOCl
28H
2O is made into the aqueous solution that concentration is 0.5～2.5mol/L, in zirconium oxychloride aqueous solution in the water soluble salt of needed alkaline-earth metal of adding or rare earth metal one or more, add additives polyethylene glycol 20～50ml by every liter of zirconium oxychloride aqueous solution again, at last with concentration be the volatile salt of 0.5～3mol/L or ammonium bicarbonate aqueous solution by requirement 100～105% with above-mentioned mixing solutions reaction, after thorough washing filters, obtain the mixture of zirconium carbonate or zirconyl carbonate and alkaline-earth metal, rare earth metal carbonate sediment; Perhaps,
Method three, with zirconium oxychloride ZrOCl
28H
2O is made into the aqueous solution that concentration is 0.5～2.5mol/L, at zirconium oxychloride ZrOCl
28H
2Press 100～105% of requirement in the O aqueous solution and add volatile salt or bicarbonate of ammonia, generate zirconium carbonate or zirconyl carbonate throw out, through washing, filtration, till detecting less than chlorion with Silver Nitrate, gained zirconium carbonate or zirconyl carbonate throw out water are sized mixing standby;
And then add excessive bicarbonate of ammonia and zirconium carbonate or zirconyl carbonate throw out are transformed generate zirconium carbonate ammonium, in zirconium carbonate ammonium solution, add additives polyethylene glycol, be heated to 85～95 ℃ and decompose generation zirconium carbonate or zirconyl carbonate, the sedimentary weight ratio of additives polyethylene glycol and zirconium carbonate or zirconyl carbonate is 40～60: 1000, and the zirconium carbonate throw out after the filtration is sized mixing with deionized water; Again with oxide compound, oxyhydroxide, the carbonate of alkaline-earth metal, rare earth metal or aluminium, or one or more mixing in the aluminium carbonate ammonium;
The second, the above-mentioned mixture that makes was carried out stirring ball-milling 30～60 minutes;
Three, spray-drying process; Adopt centrifugal or press spray drying plant, spray-dired heating temperature of inlet air is 180～300 ℃, and temperature out is 105～220 ℃; In the spraying drying jar, collect powder, send thermal treatment after screening, fine-graded dried powder then utilizes the cyclonic separation dust-precipitator that links to each other with the spraying drying jar and bagroom to collect, return with the next batch material mixed after, the ball milling batching is carried out spray-drying process once more; The primary particle of agglomerate type powder is a nanostructure, and the coacervate granularity then is a micron granularity, and the main body size range is 10～100 μ m, is shaped as sphere or class sphere;
Four, thermal treatment through 350～400 ℃ of following thermal treatments after 3～5 hours, is warming up to 700～850 ℃ and be incubated 12～16 hours in electric furnace, obtain the nano zircite ZrO of doping different substances
2Or the nano rare earth zirconate RE of pyrochlore-type crystalline structure
2Zr
2O
7Agglomerate type powder, wherein nano rare earth zirconate RE
2Zr
2O
7Only contain rare earth, and alkali-free soil and aluminium element, RE: the Zr mol ratio is controlled at 1～1.05: in 1 scope, the zirconium compounds powder inside of these nanostructures has vesicular structure, is adapted to heat barrier coat material.
2. preparation method according to claim 1 is characterized in that nano zircite ZrO
2In adulterated alkaline-earth metal, rare earth metal and light metal element be calcium Ca, magnesium Mg, yttrium Y, lanthanum La, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, ytterbium Yb, and among the aluminium Al one or more.
3. preparation method according to claim 1 is characterized in that at nano rare earth zirconate RE
2Zr
2O
7In the agglomerate type powder, RE is one or more among yttrium Y, lanthanum La, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er or the ytterbium Yb.
4. preparation method according to claim 1 is characterized in that when mixing aluminium element, and pseudo-boehmite, boehmite, aluminium hydroxide water are sized mixing, and the aqueous nitric acid that dropwise added 1: 1 is regulated pH value of slurry, till some one-tenth colloid of pH value 1.5～4; Or be raw material with the aluminium carbonate ammonium, directly mixing with zirconium carbonate or zirconyl carbonate, aluminum content counts 0.5～5% by aluminum oxide.
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