CN105621480B - A kind of method that use low temperature calcination zirconium colloidal sol prepares Zirconium dioxide nano powder - Google Patents
A kind of method that use low temperature calcination zirconium colloidal sol prepares Zirconium dioxide nano powder Download PDFInfo
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 66
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011858 nanopowder Substances 0.000 title claims abstract description 35
- 238000001354 calcination Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001868 water Inorganic materials 0.000 claims abstract description 28
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910009112 xH2O Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 claims description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 2
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 claims description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 2
- 239000000443 aerosol Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 210000005056 cell body Anatomy 0.000 claims description 2
- 235000011194 food seasoning agent Nutrition 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 7
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005119 centrifugation Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000011017 operating method Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- HNHMZSPNOIWDEN-UHFFFAOYSA-N O.[O-2].[Zr+4].[Cl+] Chemical compound O.[O-2].[Zr+4].[Cl+] HNHMZSPNOIWDEN-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910006220 ZrO(OH)2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- -1 hafnium alkoxide Chemical class 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of method that use low temperature calcination zirconium colloidal sol prepares Zirconium dioxide nano powder.Using water-soluble zirconium inorganic salts as raw material, it is dissolved in deionized water；Alkaline precipitating agent generation suspension is added, is precipitated by centrifugation or filtering；Monoacid or monoacid and dioxygen water mixed liquid are added into precipitation, the zirconium sol precursor clarified after dispergation is stirred continuously；The interval calcining and decomposing of different temperatures will be finally selected after zirconium sol precursor drying and dehydrating, the amorphous Zirconium dioxide nano powder of amorphous can either be obtained, also the stable Zirconium dioxide nano powder of Tetragonal can be kept by resulting in non-impurity-doped, and the average grain diameter of powder is can be controlled between 3 10nm.High-performance Zirconium dioxide nano powder preparation method proposed by the present invention has advantages below：The particle diameter of powder is small, narrowly distributing, good dispersion；Raw materials used reagent is easy to get and cheap；Equipment requirement and operating procedure are simple, and energy consumption is low, pollution-free, it is easy to accomplish industrial production.
Description
Technical field
The invention belongs to technical field of material, it is related to one kind and high-purity, ultra-fine, nothing is prepared using low temperature calcination zirconium colloidal sol
The method of the Zirconium dioxide nano powder for Tetragonal stabilization of adulterating.
Background technology
Zirconium dioxide (ZrO2) there is unique physics and chemical property, such as good both thermally and chemically stability, height
Intensity and fracture toughness, low heat conductivity and good wear resistance and corrosion resistance etc., thus except being used for traditional fire resisting
Outside material, the function ceramics such as piezo component, ceramic capacitor field is also widely used in, and advanced structural ceramic, function are applied
The fields such as layer, lambda sensor and catalyst carrier.
Zirconium dioxide (ZrO2) there are three kinds of stable crystal forms:Monoclinic phase (monoclinic), Tetragonal (tetragonal) and
Emission in Cubic (cubic).The form that zirconium dioxide block materials are stabilized at normal temperatures and pressures is monoclinic phase (space group P21/
c)；It is warming up to 1343K and changes into Tetragonal (P42/nmc)；Continue to be warming up to 2643K and be converted into Emission in Cubic (Fm-3m).
Zirconium dioxide (ZrO2) in heating up process, by the opposite Tetragonal of monocline and cubic phase transition, along with body
Product is shunk, and the then opposite generation volumetric expansion in cooling procedure, and the change of volume easily causes the cracking of product.Therefore, exist
Need to stablize Tetragonal or Emission in Cubic in practical application, it is not occurred Volume Changes, so as to prevent product from ftractureing.
On the other hand, the hardness and Young's modulus of four directions and cube high temperature phase zircite are higher than monoclinic phase, and have
Unique property, such as high intensity and fracture toughness and good thermal shock resistance, are that mechanical property index is outstanding, manage
The structural ceramic material thought.
In order that the Tetragonal or Emission in Cubic of zirconium dioxide keep stable in the range of relatively low service temperature, at present generally
Using the method burnt altogether after the element such as appropriate doping Y, Ce, Mg, Ca in powder.If in addition, the crystal grain of zirconium dioxide is big
It is small to be reduced to below certain nanoscale, due to surface can effect can also realize the steady of Tetragonal or Emission in Cubic at normal temperatures
Fixed, the realization of this method is firstly the need of ZrO2The average grain diameter of powder is less than 10 nanometers.
On the other hand, metal surface ZrO is being prepared2It is thermal boundary, wear-resisting when undermining corrosion-resistant functional coating, it is also desirable to use grain
Footpath is uniform, the ZrO of high pure and ultra-fine2Nano-powder is as raw material, to realize to the low temperature crystallized of ceramic coating, high-compactness and strong
Requirement in terms of adhesive force, and other physical and chemical properties optimization.
The preparation method for having invented a variety of Zirconium dioxide nano powders is studied so far, such as coprecipitation, hydro-thermal method, altogether
Precipitation-gel method, sol-gel methods, alcohol-water solution method, microemulsion method etc..But, the powder prepared by these methods is minimum
Particle diameter is between 5-50nm, and average grain diameter is typically greater than 10nm；The phase structure of powder is usually Tetragonal and list during non-impurity-doped
The mixed phase of monoclinic phase could finally realize the stabilization of Tetragonal or Emission in Cubic, it is necessary to mix Y, Ce, Mg, Ca etc..On the other hand, adopt
The zirconium precursor body obtained with these methods, such as Zr (OH)4、ZrO(OH)2And ZrOC2O4·2H2O etc., is generally required more than 600
DEG C -700 DEG C of high-temperature calcination could be decomposed completely obtains zirconium dioxide powder, thus energy consumption is higher.
Kai Jiang et al. are in " Low-Energy Path to Dense HfO2 Thin Films with Aqueous
A kind of pure water base HfO is reported in Precursor, Chemistry of materials, 23 (4), 945-952 (2011) "2It is molten
The preparation method of glue, this method is avoided using expensive hafnium alkoxide, with cheap water-soluble HfOCl2·8H2O is initiation material,
Obtaining Hf (OH)4Nitric acid is added after hydrate deposition and dispergation reaction occurs for dioxygen water mixed liquid, colloidal particle is finally given
Hafnium sol precursor less than 2nm；But the application of such a colloidal sol only is confined to prepare microelectronics and optics by this article author
HfO needed for device2Nano thin-film.Above-mentioned pure water base sol-gel methods are extended to ZrO by the present invention2The preparation of colloidal sol, passes through
Dehydration is dried to zirconium colloidal sol and low temperature calcination decomposition is prepared high-purity, ultra-fine and non-impurity-doped and can kept in the range of room temperature
The Zirconium dioxide nano powder of stable Tetragonal.
The content of the invention
The present invention provides a kind of use low temperature calcination zirconium colloidal sol and prepares the stable dioxy of high-purity, ultra-fine, non-impurity-doped Tetragonal
Change the method for zirconium nano-powder, the average particle diameter size of Zirconium dioxide nano powder is reduced to below 10nm, is not required to by this method
Adulterated the elements such as Y, Ce, Mg, Sr, Ca, and the Tetragonal two being stabilized at room temperature can be accessed by only relying on surface energy effect
Nm-class powder of zirconium oxide；Simultaneously by controlling the calcining and decomposing temperature after zirconium sol precursor drying and dehydrating, this method can also be obtained
Obtain the Zirconium dioxide nano powder of amorphous amorphous phase.
In order to achieve the above object, technical scheme is mainly included the following steps that：
The first step, prepares zirconium sol precursor
Zirconium inorganic salts are dissolved in the water, alkaline precipitating agent generation suspension is added, control pH value is more than 7.0；Suspension
Zr (OH) is obtained after centrifugation or filtering4Hydrate deposition, water washing and precipitating removes water-solubility impurity ion；One is added in precipitation
First acid adds monoacid and dioxygen water mixed liquid, and dispergation reaction occurs for precipitation, and control monoacid or monoacid are mixed with hydrogen peroxide
The addition of liquid is closed, makes 1.0<NO3 -:Zr4+<2.0, the clear zirconium that colloidal particle particle diameter≤2nm is obtained after being stirred continuously is molten
Glue presoma, it is ensured that clear sol pH value is less than 1.0.Described zirconium inorganic salts are ZrOCl2·8H2O、Zr(NO3)4·xH2O、
ZrO(NO3)2·xH2O or ZrCl4、Zr(SO4)2In one kind；Described alkaline precipitating agent is NH3·H2O, NaOH, KOH, urea
Or one kind in ammonium hydrogen carbonate；Described monoacid includes HNO3, HCOOH, HA or HAO4Wherein, A is Cl, Br, I.
Second step, prepares zirconium xerogel
Zirconium sol precursor is obtained into zirconium xerogel after room temperature to drying and dehydrating between 180 DEG C；Room temperature to 180 DEG C it
Between, drying and dehydrating process, correspondence Free water and the volatilization for combining water occur for the zirconium sol precursor of clarification.Before described zirconium colloidal sol
Drive soma drying method and be directly concentrated and dried method, aerosol spray seasoning or colloidal sol drop freeze-drying including colloidal sol.At 200 DEG C
With 250 DEG C of thermal decomposition processes of zirconium xerogel presoma generation nearby, correspondence nitrate anion and decomposition hydroxy.
3rd step, low temperature calcination prepares Zirconium dioxide nano powder
Zirconium xerogel calcining and decomposing between 280 DEG C to 380 DEG C, obtains the zirconium dioxide nanometer powder of amorphous amorphous phase
Body；Zirconium xerogel calcining and decomposing between 380 DEG C to 415 DEG C, obtains the zirconium dioxide that amorphous amorphous phase and four directions are mixed
Nano-powder；Zirconium xerogel calcining and decomposing between 415 DEG C to 750 DEG C, obtains having without doping and stablizes tetragonal phase structure
High-purity zirconium dioxide nano-powder.Described Zirconium dioxide nano powder, its chemical composition is pure ZrO2, grain size scope
For 3-10 nanometers, and stable tetragonal phase structure can be obtained at room temperature without element dopings such as Y, Ce, Mg, Sr, Ca.
Based on the above method, directly selecting property Y, Mg, Ce, Sr, Ca etc. can be added in zirconium sol precursor
The water soluble salt of multiple element or its solution, such as Y (NO3)3·6H2O、Mg(NO3)2Deng then drying and forging by colloidal sol
Burn and decompose, you can obtain the Zirconium dioxide nano powder of the element dopings such as Y, Mg, Ce, Sr, Ca.
Low, the labile chemical characteristic of energy is combined based on the zirconium complex sol precursor containing peroxy, passed through
Dehydration is dried to zirconium colloidal sol and low temperature calcination decomposition is prepared Zirconium dioxide nano powder and had the beneficial effect that：(1) low temperature
Zirconium dioxide nano powder prepared by calcination method has high-purity, ultra-fine and can kept without stabilizer doping in the range of room temperature
The feature of stable Tetragonal；Because the average particle diameter size of Zirconium dioxide nano powder is between 3-10nm, according to surface efficiency
Should, it is the zirconium dioxide that can obtain stablizing Tetragonal without element dopings such as Y, Ce, Mg, Sr, Ca；(2) in zirconium sol precursor
In can directly add the water soluble salt or its solution of the multiple elements such as Y, Ce, Mg, Sr, Ca, subsequent drying sol dehydration and
Calcining and decomposing can obtain the mixed uniformly Zirconium dioxide nano powder of the accurate adjustable and atom level of doping, so as to meet difference
Application demand；(3) simple to production environment requirement and device requirement, energy consumption is low, and the cycle is short；With water-soluble zirconium cheap and easy to get without
Machine salt is raw material, it is to avoid using expensive zirconium organic alkoxide, production cost is low.Preparation technology has simple to operate and free of contamination
Feature, it is adaptable to the industrialized production of zirconia nanocrystals ceramics, fiber and a variety of functional coatings.
Brief description of the drawings
Fig. 1 is the process chart of the present invention；
Fig. 2 is that the thermal weight loss and DSC of zirconium sol precursor prepared by embodiment 1-4 inhale Heat release analysis curve map.
Fig. 3 is X ray diffracting spectrum of the zirconium xerogel prepared in embodiment 1 after 330 DEG C of calcining and decomposings；
Fig. 4 is X ray diffracting spectrum of the zirconium xerogel prepared in embodiment 2 after 405 DEG C of calcining and decomposings；
Fig. 5 is X ray diffracting spectrum of the zirconium xerogel prepared in embodiment 3 after 430 DEG C of calcining and decomposings；
Fig. 6 is the transmission electron microscope shape appearance figure of the Zirconium dioxide nano powder after 430 DEG C of calcining and decomposings in embodiment 3.
Embodiment
From figure 2 it can be seen that several main peaks that DSC curve occurs are all relative with the obvious mass loss of TGA curves
Should.The quick volatilization of Free water and combination water in two endothermic peaks difference counter sample near 100 DEG C, 200 DEG C and 250 DEG C attached
Two endothermic peaks closely occurred correspond to nitrate anion and decomposition hydroxy respectively, and the exothermic peak occurred near 450 DEG C is corresponding
In powder by amorphous amorphous state crystallization be Tetragonal ordered structure.With reference to the accompanying drawings 2, it is heated to the Free water in 180 DEG C of colloids
It can all be vapored away with reference to water, be changed into xerogel；Occur respectively near 200 DEG C and 250 DEG C nitrate anion in xerogel and
Intensive decomposition hydroxy, so calcining heat is not pure ZrO2 less than 280 DEG C of obtained powders, two be containing nitrate anion and hydrogen
The Zr compounds of oxygen root.
Embodiment 1：
Chlorine hydrate zirconium oxide is dissolved in the settled solution that deionized water formation concentration is 0.12mol/L, then added
1mol/L ammoniacal liquor formation suspension, measurement pH value is 7.8；Suspension obtains Zr (OH) after centrifugation4Hydrate deposition, washing
Precipitation removes removing chloride；Solved then to the dioxygen water mixed liquid of nitric acid and 10mol/L that 2mol/L is quantitatively adding in precipitation
Glue reacts；The zirconium sol precursor that high degree of agitation can be clarified for 1 day, it is 0.8 to measure clear sol pH value.
The zirconium sol precursor of clarification is filtered, removing may undissolved precipitation particle；Then heat and steam at 70 DEG C
Shampoo point, obtains transparence zirconium xerogel.Zirconium xerogel is obtained the two of amorphous amorphous state at 330 DEG C after calcining and decomposing
Nm-class powder of zirconium oxide.
As can be seen that only in tetragonal zirconium dioxide (101) and (200) two most from the X ray diffracting spectrum of accompanying drawing 3
Occurs the peak type of two disperses in the range of strong peak corresponding angle, it is amorphous amorphous state to show powder main body.
Case study on implementation 2：
Chlorine hydrate zirconium oxide is dissolved in the settled solution that deionized water formation concentration is 0.12mol/L, then added
1mol/L ammoniacal liquor formation suspension, measurement pH value is 9.0；Suspension obtains Zr (OH) after filtering4Hydrate deposition, washing
Precipitation removes removing chloride；Solved then to the dioxygen water mixed liquid of nitric acid and 10mol/L that 2mol/L is quantitatively adding in precipitation
Glue reacts；The zirconium sol precursor that high degree of agitation can be clarified for 1 day, it is 0.6 to measure clear sol pH value.
The zirconium sol precursor of clarification is filtered, removing may undissolved precipitation particle；Then heat and steam at 75 DEG C
Shampoo point, obtains transparence zirconium xerogel.Zirconium xerogel is obtained into amorphous amorphous state and four at 405 DEG C after calcining and decomposing
The Zirconium dioxide nano powder that side is mixed.
As can be seen that in tetragonal zirconium dioxide (101), (200) and (211) three from the X ray diffracting spectrum of accompanying drawing 4
There is somewhat sharp peak type in the range of individual highest peak corresponding angle, shown that powder has been partially converted into Tetragonal.
Case study on implementation 3：
Chlorine hydrate zirconium oxide is dissolved in the settled solution that deionized water formation concentration is 0.12mol/L, then added
1mol/L ammoniacal liquor formation suspension, measurement pH value is 8.5；Suspension obtains Zr (OH) after centrifugation4Hydrate deposition, washing
Precipitation removes removing chloride；Solved then to the dioxygen water mixed liquid of nitric acid and 10mol/L that 2mol/L is quantitatively adding in precipitation
Glue reacts；The zirconium sol precursor that high degree of agitation can be clarified for 1 day, it is 0.7 to measure clear sol pH value.
The sol precursor of clarification is filtered, removing may undissolved precipitation particle；Then the heating evaporation at 80 DEG C
Moisture, obtains transparence zirconium xerogel.Xerogel finally is obtained stablizing to the dioxy of Tetragonal at 430 DEG C after calcining and decomposing
Change zirconium nano-powder.
As can be seen that powder complete crystallization is stable tetragonal phase structure, diffraction from the X ray diffracting spectrum of accompanying drawing 5
Peak is clearly bright and sharp, does not occur other impurities peak and zirconium dioxide monoclinic phase diffraction maximum.Its correspondence standard PDF card is JCPDS:
42-1164.The average grain diameter about 5nm of powder, and favorable dispersibility are can be seen that from the TEM shape appearance figures of the powder of accompanying drawing 6.
Case study on implementation 4：
Chlorine hydrate zirconium oxide is dissolved in the settled solution that deionized water formation concentration is 0.12mol/L, then added
1mol/L ammoniacal liquor formation suspension, measurement pH value is 8.0；Suspension obtains Zr (OH) after filtering4Hydrate deposition, washing
Precipitation removes removing chloride；Solved then to the dioxygen water mixed liquid of nitric acid and 10mol/L that 2mol/L is quantitatively adding in precipitation
Glue reacts；The zirconium sol precursor that high degree of agitation can be clarified for 1 day, it is 0.7 to measure clear sol pH value.
Weigh Y (NO3)3·6H2O water soluble salts are dissolved in zirconium sol precursor, control Y3+:Zr4+=0.08:1, and magnetic force
Stirring 1 minute, forms the clear sol precursor that Y dopings are 8%.The sol precursor of clarification is heated at 85 DEG C
Moisture is evaporated, xerogel is obtained；Finally by xerogel at 430 DEG C calcining and decomposing, produce the stable ZrO of 8%Y2(YSZ) Emission in Cubic
Nano-powder.
Claims (9)
1. a kind of method that use low temperature calcination zirconium colloidal sol prepares Zirconium dioxide nano powder, it is characterised in that including following step
Suddenly：
The first step, prepares zirconium sol precursor
Zirconium inorganic salts are dissolved in the water, alkaline precipitating agent generation suspension is added；Suspension is centrifuged or precipitated after filtering,
Water washing and precipitating removes water-solubility impurity ion；Monoacid is added in precipitation or the mixed liquor of monoacid and hydrogen peroxide is added, and is stirred
Clear zirconium sol precursor is obtained after mixing；
Second step, by zirconium sol precursor before room temperature obtains zirconium xerogel, described zirconium colloidal sol to drying and dehydrating between 180 DEG C
Drive soma drying method and be directly concentrated and dried method, aerosol spray seasoning or colloidal sol drop freeze-drying including colloidal sol；
3rd step, low temperature calcination zirconium xerogel prepares Zirconium dioxide nano powder
Zirconium xerogel obtains the Zirconium dioxide nano powder of amorphous amorphous phase in 280 DEG C~380 DEG C calcining and decomposings；Zirconium is dry solidifying
Glue obtains the Zirconium dioxide nano powder that amorphous amorphous phase and four directions are mixed in 380 DEG C~415 DEG C calcining and decomposings；Zirconium is done
Gel obtains having the high-purity zirconium dioxide nanometer for stablizing tetragonal phase structure without doping in 415 DEG C~750 DEG C calcining and decomposings
Powder.
2. according to the method described in claim 1, it is characterised in that described zirconium inorganic salts are ZrOCl2·8H2O、Zr
(NO3)4·xH2O、ZrO(NO3)2·xH2O or ZrCl4、Zr(SO4)2In one kind.
3. method according to claim 1 or 2, it is characterised in that described alkaline precipitating agent is NH3·H2O、NaOH、
One kind in KOH, urea or ammonium hydrogen carbonate.
4. method according to claim 1 or 2, it is characterised in that described monoacid is HNO3, HCOOH, HA or HAO4,
Wherein, A is Cl, Br, I.
5. method according to claim 3, it is characterised in that described monoacid is HNO3, HCOOH, HA or HAO4, its
In, A is Cl, Br, I.
6. the method according to claim 1 or 2 or 5, it is characterised in that directly selecting property adds in zirconium sol precursor
Enter Y, Mg, Ce, Sr, Ca water soluble salt or its solution, decomposed by the drying and calcination of zirconium sol precursor, obtain element and mix
Miscellaneous Zirconium dioxide nano powder.
7. method according to claim 3, it is characterised in that in zirconium sol precursor directly selecting property add Y,
Mg, Ce, Sr, Ca water soluble salt or its solution, are decomposed by the drying and calcination of zirconium sol precursor, obtain element doping
Zirconium dioxide nano powder.
8. method according to claim 4, it is characterised in that in zirconium sol precursor directly selecting property add Y,
Mg, Ce, Sr, Ca water soluble salt or its solution, are decomposed by the drying and calcination of zirconium sol precursor, obtain element doping
Zirconium dioxide nano powder.
9. the Zirconium dioxide nano powder prepared using the method described in claim 1, it is characterised in that described zirconium dioxide
Nano-powder, chemical composition is pure ZrO2, grain size scope is 3-10 nanometers, and can be protected at room temperature without element doping
Keep steady and determine tetragonal phase structure.
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