CN103242039B - Synthesis method of nanometer yttrium-stabilized zirconia - Google Patents
Synthesis method of nanometer yttrium-stabilized zirconia Download PDFInfo
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Abstract
The invention discloses a synthesis method of nanometer yttrium-stabilized zirconia. The method comprises the following steps of: a) mixing ZrOCl2 containing 2 to 6 percent of ZrO2 with 6 to 9 percent Na2SO4, adding hydrochloric acid and adjusting the acid concentration of the solution system to be 0.5 to 1.2 mol/L; b) heating the mixed solution obtained in the step a) to 40 to 85 DEG C to generate sol; c) adding NaOH solution into the sol for at least twice to adjust the pH value to obtain precipitate; d) filtering the precipitate to obtain a pulp cake, and pulping and washing the pulp cake until the pulp is neutral; e) adding Y(NO3)3 containing 6 to 10 percent of Y2O3 into the neutral pulp obtained in the step d), heating the solution to 60 to 90 DEG C, adding NaOH to adjust the pH value of the solution system to be 8.7 to 9.3 to obtain composite precipitate; f) filtering the obtained composite precipitate, adding deionized water, and pulping and washing until the pulp is neutral; and g) filtering the neutral pulp obtained in the step f) to obtain a pulp cake and calcining to obtain nanometer yttrium-stabilized zirconia powder. According to the synthesis method, the technical process is simple, and the prepared powder is small in crystalline grain, uniform in granularity, narrow in grain distribution and large in specific surface area.
Description
Technical field
The present invention relates to a kind of zirconic synthetic method, particularly relate to a kind of synthetic method of nanometer yttrium stable zirconium oxide.
Background technology
The oxide compound of zirconium is a kind of very important metal oxide, Y
2o
3stablize ZrO
2material melting point is up to 2700 DEG C, and thermal conductivity is low, and its thermal conductivity is minimum in common stupalith, and especially, in the time of 1000 DEG C of high temperature, its heat conductivity value is minimum in all dense ceramic material (2.3W/ (m.K)).The in the situation that of pore and crackle existence, Y
2o
3stablize ZrO
2the heat conductivity value of material is conventionally between 0.8-1.7W/ (m. K); Its thermal expansivity only 9 × 10
-6-11.5 × 10
-6/ K, this and metallic substance approach.ZrO
2excellent high high-temp stability and heat-proof quality have ensured when it is at high temperature applied more stable, suitable ceramic coating and high-temperature flame-proof goods and the important structural ceramic material done.Its chemical stability is high, and etch resistant properties is good, especially has the ability of chemical resistance of concrete and microbial attack, except H
2sO
4outside HF, acid, alkali and alkali fusion body, glass melt and molten metal are all had to good stability.From structure, ZrO
2because it has acid and basic surface center, because of but a kind of desirable soda acid base double-function catalyzing material play an important role at catalytic field especially solid caustic soda catalytic field.It also has unique transformation toughening, and this makes ZrO
2pottery not only intensity is high, and fracture toughness property is also very large, becomes important structural ceramic material.Meanwhile, ZrO
2there is high temperature oxygen ionic conductivity, can be applied in oxygen sensor.In solid oxygen fuel cell, adopt ZrO
2stupalith is made ionogen, is a kind of new technology that is converted into electric energy with the energy that conventional oil hydrogen or hydrocarbon polymer react discharged with oxygen.Generally speaking, owing to thering is good machinery, calorifics, electricity, optical property, ZrO
2all have a wide range of applications and study at aspects such as high-temperature structural material, High Temperature Optical element, oxygen photosensitive elements, fuel cells.
Yttrium oxide (Y
2o
3molar fraction is 6-10%) stable zirconium white (YSZ) is used as the ionogen of Solid Oxide Fuel Cell (SOFC) commonly, because it has high oxygen ionic conductivity and is all quite stable in the atmosphere of oxygenant and fuel.
The zirconium white of stabilized nano yttrium oxide is that YSZ powder preparation method mainly contains at present: coprecipitation method, sol-gel method, co-precipitation-gel method, metal alkoxide hydrolysis method, hydrothermal method, emulsion method.Other also have microwave assisting method, carbohydrate gum-nitrate method, glycine-nitrate method, certainly spread method etc.Coprecipitation process is simple, gained nano-powder better performances, but coprecipitation method is difficult to control each component precipitation from homogeneous solution, adopts ammoniacal liquor also can cause topsoil as precipitation agent.Tradition sol-gel method throughput is little, and raw materials cost is high and environment is had to pollution, and micelle formation and gel-filtration, washing process are wayward, and the nano particle diameter wider distribution of preparation, easily reunites in sintering process.There is coprecipitation method shortcoming in co-precipitation-gel method, can to environment equally.Metal alkoxide hydrolysis method need to be used a large amount of expensive organometallic compounds, and cost is large; And be often some poisonous materials as the organism of solvent, easily pollute problem.Hydrothermal method needs high-purity starting material and the equipment of high temperature high voltage resistant, is unfavorable for reducing production costs.Emulsion method can be controlled granular size, narrow particle size distribution, but production process complexity, and cost is high.
CN102874869A discloses a kind of yttrium stable zirconium oxide preparation method, and the method is a kind of multistage emulsion method, need to add the organism such as dimethylbenzene, and environmental pollution is comparatively serious.
The coating that CN102765935A discloses yttrium oxide-stabilized zirconium oxide powder and preparation method thereof and formed.The method production process is loaded down with trivial details, and relative cost is higher.
The method of CN102447125A Synthesized by Hydrothermal Method yttrium stable zirconium oxide.The method needs High Temperature High Pressure, higher to equipment requirements.
CN101708829A discloses a kind of yttria-stabilized zirconia powder preparation method, and this method is ultrasonic-microwave synthesis method, carries out precursor preparation under ultrasound condition.The method is higher to equipment requirements equally, and cost is higher.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic method of nanometer yttrium stable zirconium oxide, and this synthetic method craft is simple, and the nanometer yttrium stable zirconium oxide powder crystal grain making is tiny, be about 10-30nm, epigranular and narrowly distributing, specific surface area is high, can reach 70-110 m
2/ g.
For solving the problems of the technologies described above, the invention provides a kind of synthetic method of nanometer yttrium stable zirconium oxide, wherein, this synthetic method comprises the steps:
A) Na that is 6-9% by mass concentration
2sO
4the aqueous solution and ZrO
2mass content is the ZrOCl of 2-6%
2the aqueous solution is pressed Na
2sO
4and ZrO
2mol ratio is that 0.375-0.9 mixes, and in solution, adds hydrochloric acid, the acid concentration of solution system is adjusted to 0.5-1.2mol/L, preferably 0.6-0.8 mol/L;
B) mixing solutions after hydrochloric acid regulates step a) being obtained is warmed up to 40-85 DEG C, is preferably 60-80 DEG C, and insulation generates colloidal sol;
C) in the colloidal sol obtaining to step b), add the pH value of at least twice NaOH solution regulation system, in the colloidal sol obtaining to step b) for the first time, add NaOH solution, obtain primary sedimentation, in system, continue to add NaOH solution afterwards, obtain secondary sedimentation, add the final pH value of NaOH solution system to be adjusted to 8.7-9.3 through at least twice;
D) sedimentation and filtration step c) finally being obtained obtains starching cake, adds deionized water to break into slurries washing slurry cake and makes slurries system become neutral;
E) by Y
2o
3mass content is the Y (NO of 6-10%
3)
3the aqueous solution joins in the neutral slurries that step d) obtains, wherein, and Y in solution system
2o
3and ZrO
2mol ratio be 6-10:94-90, solution is warming up to 60-90 DEG C, add the pH value of NaOH solution regulator solution system to 8.7-9.3, obtain composite precipitation;
F) composite precipitation step e) being obtained filters and obtains starching cake, adds deionized water to break into slurries washing and makes slurries system become neutral;
G) the neutral slurries that step f) obtained filter and obtain starching cake, and slurry cake obtains nanometer yttrium stable zirconium oxide powder through calcining.
The synthetic method of above-mentioned nanometer yttrium stable zirconium oxide, wherein, the hydrochloric acid adding in described step a) is that mass concentration is 37% concentrated hydrochloric acid.
The synthetic method of above-mentioned nanometer yttrium stable zirconium oxide, wherein, in described step c), in the colloidal sol obtaining to step b), add the pH value of at least twice NaOH solution regulation system, be precipitated, while adding NaOH solution, make system be warming up to 70-90 DEG C at every turn, to be conducive to generate precipitation.
The synthetic method of above-mentioned nanometer yttrium stable zirconium oxide, wherein, in described step c), in the colloidal sol obtaining to step b), add the pH value of twice NaOH solution regulation system, in the colloidal sol obtaining to step b) for the first time, add NaOH solution, the pH value of system is adjusted to 5.7-6.3, obtain primary sedimentation, in system, continue to add NaOH solution that the pH value of system is adjusted to 8.7-9.3 afterwards, obtain secondary sedimentation.
The synthetic method of above-mentioned nanometer yttrium stable zirconium oxide, wherein, in described step c), in the colloidal sol obtaining to step b), add the pH value of three NaOH solution regulation system, in the colloidal sol obtaining to step b) for the first time, add NaOH solution, the pH value of system is adjusted to 2.8-3.5, obtain primary sedimentation, in system, add for the second time NaOH solution that the pH value of system is adjusted to 5.7-6.3 afterwards, obtain secondary sedimentation, continue to add NaOH solution that the pH value of system is adjusted to 8.7-9.3 in system, obtain precipitation three times.
The synthetic method of above-mentioned nanometer yttrium stable zirconium oxide, wherein, the NaOH solution adding in described step c) and step e) is that mass concentration is 30% industrial sodium hydroxide.
The synthetic method of above-mentioned nanometer yttrium stable zirconium oxide, wherein, described step d) and f) in add deionized water to break into after slurries slurry cake, slurries are warming up to 50-70 DEG C of washing and make slurries system become neutral, intensification can be accelerated washing speed, shortens slurries are washed into the neutral time.
The synthetic method of above-mentioned nanometer yttrium stable zirconium oxide wherein, is calcined slurry cake and within 3-6 hour, is obtained nanometer yttrium stable zirconium oxide powder in described step g) at 600 DEG C.
The synthetic method of nanometer yttrium stable zirconium oxide of the present invention, first by ZrOCl
2the aqueous solution and Na
2sO
4aqueous solution, the acid concentration of the employing hydrochloric acid hierarchy of control, heats up and obtains colloidal sol.The acid concentration of system is most important for plastic, if system acid concentration is too low, is difficult to plastic under low temperature environment, if the acid concentration of system is too high, makes powder characteristic poor, is unsuitable for high-end applications.In the colloid obtaining, gradation adds NaOH solution, make colloid experience at least twice precipitation process, repeatedly precipitation can be controlled colloid and progressively grows up, can make the powder crystal grain that obtains tiny and be evenly distributed, avoid precipitation too fast, so that micelle is grown up rapidly, prepare crystal grain powder large and that easily reunite.In colloid, gradation adds NaOH solution, and the adjusting of the pH value of the NaOH solution at every turn adding to system is without particular determination, as long as the pH value of system is adjusted to 8.7-9.3 the most at last.After the sedimentation and filtration obtaining is washed, with the compound composite precipitation that obtains of yttrium, filtration washing is to neutrality, and calcining obtains nanometer yttrium stable zirconium oxide powder.Synthetic method of the present invention is by controlling ZrOCl
2and Na
2sO
4acid concentration, plastic temperature, the final pH value of plastic system and the method that colloid is repeatedly precipitated of mixing solutions, effectively controlled plastic process, made the nanometer yttrium stable zirconium oxide powder of excellent performance.
The synthetic method of nanometer yttrium stable zirconium oxide of the present invention, for preparation nanometer yttrium stable zirconium oxide powder provides brand-new preparation method, whole technological process is simple, easily operation, the nanometer yttrium stable zirconium oxide powder crystal grain making is tiny, is about 10-30nm, epigranular and narrowly distributing, specific surface area is high, can reach 70-110 m
2/, can be used in the high-end demand to nanometer yttrium stable zirconium oxide, as prepare solid-oxide fuel battery electrolyte material.
Embodiment
Describe the present invention in detail below by embodiment.
Embodiment 1
A) Na that is 7.3% by mass concentration
2sO
4the aqueous solution and ZrO
2mass content is 4% ZrOCl
2the aqueous solution is pressed Na
2sO
4and ZrO
2mol ratio is 0.6 mixing, is that concentration of hydrochloric acid is adjusted to 0.8mol/L to the concentrated hydrochloric acid that adds 37% in solution by the acid concentration of solution system;
B) acid concentration step a) being obtained is that the mixing solutions of 0.8 mol/L is warmed up to 70 DEG C, and insulation, obtained canescence colloidal sol after 2 hours;
C) in the canescence colloidal sol obtaining to step b), add the pH value of twice NaOH solution regulation system, be 30% NaOH solution to adding mass concentration in canescence colloidal sol for the first time, the pH value of system is adjusted to 6, obtain primary sedimentation, be 30% NaOH solution to continuing to add mass concentration in system afterwards, system is warming up to 85 DEG C, and after NaOH solution regulates, the pH value of system is 9, obtains secondary sedimentation;
D) sedimentation and filtration step c) finally being obtained obtains starching cake, adds deionized water to break into slurries slurry cake, is warming up to 70 DEG C, makes slurries washing to neutral;
E) by Y
2o
3mass content is 8% Y (NO
3)
3the aqueous solution joins in the neutral slurries that step d) obtains, wherein, and Y in solution system
2o
3and ZrO
2mol ratio be 8:92, solution is warming up to 70 DEG C, adding mass concentration is the pH value to 9 of 30% NaOH solution regulator solution system, yttrium is compound to be completed, and obtains composite precipitation;
F) composite precipitation step e) being obtained filters and obtains starching cake, adds deionized water to break into slurries, is warming up to 70 DEG C, makes slurries washing to neutral;
G) the neutral slurries that step f) obtained filter and obtain starching cake, and slurry cake obtains nanometer yttrium stable zirconium oxide powder for 3 hours 600 DEG C of calcinings.
Embodiment 2-5 and comparative example 1-3, except the interior different data of table 1, preparation method is with embodiment 1.Wherein, embodiment 3,4,5 and comparative example 2 obtain after canescence colloidal sol in step b), system is warming up to 70 DEG C, add the pH value of NaOH solution regulator solution system for the first time, obtain primary sedimentation, embodiment 2 and 4 is warming up to 90 DEG C by system after completing in step c) and precipitating for the second time, add the pH value of NaOH solution regulator solution system for the third time, obtain precipitation three times.
Comparative example 4
By ZrO
2mass content is 4% ZrOCl
2the aqueous solution and Y
2o
3mass content is 8% Y (NO
3)
3aqueous solution, wherein Y in solution system
2o
3and ZrO
2mol ratio be 8:92, solution is warming up to 70 DEG C, adding mass concentration is the pH value to 9 of 30% NaOH solution regulator solution system, and yttrium is compound to be completed, and obtains composite precipitation, composite precipitation is filtered and obtains starching cake, add deionized water making beating, be warming up to 70 DEG C, make slurries washing to neutral, refilter and obtain starching cake, slurry cake obtains nanometer yttrium stable zirconium oxide powder for 3 hours 600 DEG C of calcinings.
The synthetic nanometer yttrium stable zirconium oxide powder characteristic data of embodiment 1-5 and comparative example 1-4 refer to table 1.
Table 1
Note: 1, ZrO
2mass concentration refers to ZrO
2at ZrOCl
2mass concentration in the aqueous solution;
2, Na
2sO
4mass concentration refers to Na
2sO
4at Na
2sO
4mass concentration in the aqueous solution;
3, Y
2o
3mass concentration refers to Y
2o
3at Y (NO
3)
3mass concentration in the aqueous solution;
4, HCl volumetric molar concentration (mol/L) refers to add in the step a) of embodiment 1 after concentrated hydrochloric acid regulation system acid concentration, the volumetric molar concentration of hydrochloric acid in system;
5, plastic temperature refers to the temperature in step b), solution being heated up;
6, precipitation frequency n and pH value refer to that the number of times and the each precipitation that in step c), add NaOH solution to generate precipitation regulate through NaOH solution the system pH obtaining.
The nanometer yttrium stable zirconium oxide powder that synthetic method of the present invention makes, crystal grain is little, is about 10-30nm, and specific surface area is high, can reach 70-110 m
2/ g, even particle distribution, this powder is applicable to the high-end demand to nanometer yttrium stable zirconium oxide powder, for example, prepare solid-oxide fuel battery electrolyte.Method of the present invention is raw materials used to be easy to get, not high to equipment requirements, with low cost, is easy to industrial production.
Claims (9)
1. a synthetic method for nanometer yttrium stable zirconium oxide, wherein, this synthetic method comprises the steps:
A) Na that is 6-9% by mass concentration
2sO
4the aqueous solution and ZrO
2mass content is the ZrOCl of 2-6%
2the aqueous solution is pressed Na
2sO
4and ZrO
2mol ratio is that 0.375-0.9 mixes, and in solution, adds hydrochloric acid, and the acid concentration of solution system is adjusted to 0.5-1.2mol/L;
B) mixing solutions after hydrochloric acid regulates step a) being obtained is warmed up to 40-85 DEG C, and insulation generates colloidal sol;
C) in the colloidal sol obtaining to step b), add the pH value of at least twice NaOH solution regulation system, in the colloidal sol obtaining to step b) for the first time, add NaOH solution, obtain primary sedimentation, in system, continue to add NaOH solution afterwards, obtain secondary sedimentation, add NaOH solution through at least twice, the final pH value of system is adjusted to 8.7-9.3;
D) sedimentation and filtration step c) finally being obtained obtains starching cake, adds deionized water to break into slurries washing slurry cake and makes slurries system become neutral;
E) by Y
2o
3mass content is the Y (NO of 6-10%
3)
3the aqueous solution joins in the neutral slurries that step d) obtains, wherein, and Y in solution system
2o
3and ZrO
2mol ratio be 6-10:94-90, solution is warming up to 60-90 DEG C, add the pH value of NaOH solution regulator solution system to 8.7-9.3, obtain composite precipitation;
F) composite precipitation step e) being obtained filters and obtains starching cake, adds deionized water to break into slurries washing and makes slurries system become neutral;
G) the neutral slurries that step f) obtained filter and obtain starching cake, and slurry cake is calcined and within 3-6 hour, obtained nanometer yttrium stable zirconium oxide powder at 600 DEG C.
2. synthetic method as claimed in claim 1, wherein, in described step a), adds hydrochloric acid that the acid concentration of solution system is adjusted to 0.6-0.8mol/L.
3. synthetic method as claimed in claim 2, wherein, in described step b), the mixing solutions after hydrochloric acid regulates that step a) is obtained is warmed up to 60-80 DEG C.
4. synthetic method as claimed in claim 1, wherein, the hydrochloric acid adding in described step a) is that mass concentration is 37% concentrated hydrochloric acid.
5. synthetic method as claimed in claim 1, wherein, in described step c), adds the pH value of at least twice NaOH solution regulation system to step b) in the colloidal sol obtaining, be precipitated, and while adding NaOH solution, makes system be warming up to 70-90 DEG C at every turn.
6. the synthetic method as described in claim 1 or 5, wherein, in described step c), in the colloidal sol obtaining to step b), add the pH value of twice NaOH solution regulation system, in the colloidal sol obtaining to step b) for the first time, add NaOH solution, the pH value of system is adjusted to 5.7-6.3, obtain primary sedimentation, in system, continue to add NaOH solution that the pH value of system is adjusted to 8.7-9.3 afterwards, obtain secondary sedimentation.
7. the synthetic method as described in claim 1 or 5, wherein, in described step c), in the colloidal sol obtaining to step b), add the pH value of three NaOH solution regulation system, in the colloidal sol obtaining to step b) for the first time, add NaOH solution, the pH value of system is adjusted to 2.8-3.5, obtain primary sedimentation, in system, add for the second time NaOH solution that the pH value of system is adjusted to 5.7-6.3 afterwards, obtain secondary sedimentation, continue to add NaOH solution that the pH value of system is adjusted to 8.7-9.3 in system, obtain precipitation three times.
8. the synthetic method as described in claim 1 or 5, wherein, the NaOH solution adding in described step c) and step e) is that mass concentration is 30% industrial sodium hydroxide.
9. synthetic method as claimed in claim 1, wherein, described step d) and f) in add deionized water to break into after slurries slurry cake, slurries are warming up to 50-70 DEG C of washing and make slurries system become neutral.
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