CN1948163A - Preparation method of zirconium oxide colloidal sol - Google Patents
Preparation method of zirconium oxide colloidal sol Download PDFInfo
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- CN1948163A CN1948163A CN 200610154597 CN200610154597A CN1948163A CN 1948163 A CN1948163 A CN 1948163A CN 200610154597 CN200610154597 CN 200610154597 CN 200610154597 A CN200610154597 A CN 200610154597A CN 1948163 A CN1948163 A CN 1948163A
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- 238000002360 preparation method Methods 0.000 title claims description 27
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 title abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910001868 water Inorganic materials 0.000 claims abstract description 33
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000000084 colloidal system Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003754 zirconium Chemical class 0.000 claims description 8
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 26
- 238000009826 distribution Methods 0.000 abstract description 15
- 230000007062 hydrolysis Effects 0.000 abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 9
- 239000011259 mixed solution Substances 0.000 abstract description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- -1 chlorine ions Chemical class 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 20
- 239000000919 ceramic Substances 0.000 description 9
- 229910010293 ceramic material Inorganic materials 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000007858 starting material Substances 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
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Abstract
The present invention discloses a method for preparing zirconium oxide sol. Said method includes the following steps: using zirconium oxychloride as precursor body, using hydrogen peroxide as hydrolysis accelerating agent, utilizing strong oxidative property of hydrogen peroxide to make chlorine ions be reduced into chlorine gas and make said chlorine gas be overflowed so as to obtain the colloid whose particle size distribution is narrow. Said invention makes the zirconium oxychloride be dissolved in a proper quantity of mixed solution formed from alcohol, water and surfactant, uniformly mixes and stirs them, and selects proper surfactant, and utilizes a simple technological process to prepare high-purity and stable zirconium oxide sole whose particle size can be controlled and particle size distribution is narrow.
Description
Technical Field
The invention relates to the technical field of sol-gel methods, in particular to a preparation method of zirconia sol, which can be used as a precursor of high-purity nano zirconia powder and composite zirconia functional ceramics.
Background
Zirconia has found wide application in many fields due to its unique properties. ZrO (ZrO)2Is the only metal oxide with acidity, alkalinity, oxidability and reducibility, and shows unique catalytic activity and selectivity in the technical field of catalysis as a carrier or catalyst. Zirconia has excellent performances of high temperature resistance, corrosion resistance, high mechanical strength, low friction coefficient and the like, and becomes one of ceramics which are intensively researched in the field of functional materials. The structural ceramic elements prepared by the method, such as cutters, moulds, bearings, high-temperature refractory materials and the like, have excellent mechanical and physical properties. As an electronic ceramic material, a component such as a solid fuel cell, a piezoelectric ceramic, a ferroelectric ceramic, etc., made therefrom has specific electrical properties. As a multipurpose ceramic material, the purity of precursor powder is required to be high in some application fields, and the multipurpose ceramic material is required to be compounded with other materials in some fields. Ideal ZrO2The powder requirements are as follows: particle size is submicron or finer; the shape is spherical; no agglomeration; the purity is high, and the chemical composition is uniform; the particle size distribution is narrow. Wherein, the purity and the granularity are the determining factors for marking the powder property, and the high-purity, ultra-fine and high-quality ZrO is developed2The powder becomes one of the subjects of great attention of fine ceramic researchers at home and abroad. As an ideal composite ceramic material, the nano-composite ceramic material also needs quantitative doping, and the mixing uniformity can reach molecular weight, small particle size and controllable particle size.
At present, most of the methods adopted are to prepare precursor sol by a sol-gel method and then prepare powder or composite ceramic by other processes. In principle, this process is similar to the conventional powder preparation except that the appropriate process is used to produce Zr (OH)4Forming colloidal particles without formingPrecipitating, properly treating to form gel containing large amount of water, drying, dewatering, calcining and other steps to prepare high purity ZrO2Powder or composite ceramic material. The advantages are that: fine granularity, narrow granularity distribution, submicron level or finer granularity, large specific surface area and high activity; the particle morphology is equiaxed spherical; no aggregates; the chemical composition is uniform. Therefore, the sol-gel method is the most ideal and valuable powder preparation method at present. The conventional methods for preparing zirconia sol include: coprecipitation method, hydrolysis method, etc.
Coprecipitation methods are commonly used to prepare composite ceramic materials. The precipitation method commonly adopted in industry is to use alkaline liquor as a precipitation 7 agent, prepare zirconium sol by controlling the pH value, and prepare ZrO through the processes of filtering, washing, drying, calcining and the like2Compound medicineAnd mixing ceramic material powder. The commonly used precipitating agent is sodium hydroxide, potassium hydroxide, ammonia water, etc., and the zirconium salt is ZrOCl2、Zr(NO3)4The method has the advantages of simple process, convenience, easy operation and low cost; the disadvantage is that a coprecipitate with a homogeneous composition is hardly obtained and the ions introduced by the coprecipitation are not easily removed. And the powder is easy to be subjected to hard agglomeration, and the ideal granularity cannot be obtained. Although the state of agglomeration can be improved by special treatment, the advantage of simple process is lost by adding special treatment. In addition, the purity of the powder is affected by the increase of the number of process procedures and the use of reagents, and the purity of the powder is affected by the increase of impurities in the powder, and the particle size of the powder is greatly affected by the reagents.
In the conventional hydrolysis method, particles are easy to agglomerate, and the agglomeration is more serious in the separation and drying period in the later period, and when the composite ceramic is prepared, all metal oxides cannot be precipitated simultaneously or completely, so that the component deviation and the uneven distribution of chemical components are caused.
Colloids prepared by hydrolysis of organic alkoxides (Journal of Materials Research, 1991, 6(5), 1073) are not suitable for industrial production because alkoxides are very easily hydrolyzed and thereforeprocess control is difficult, and particles are small plus alkoxides are expensive.
In China, inorganic zirconium salt hydrolysis is generally adopted to prepare colloid, and a precipitator (generally ammonia water) is required to be introduced in the preparation process so that zirconium salt is hydrolyzed to form sol. For example, chinese patent 91101690.2 discloses a technique for preparing zirconia fine powder by an alcohol-adding coalescence method, wherein the precursor sol is obtained by adding ammonia water into an aqueous solution of an inorganic zirconium salt. Due to the addition of the precipitant, the colloid contains other soluble salts, and the colloid needs to be repeatedly washed, so that the subsequent powder process becomes complicated and fussy. The sol-gel method of the yttria-doped zirconia micro-filtration membrane provided by the Chinese patent 94103126.8 introduces excessive ammonia water to precipitate zirconium salt and then add hydrochloric acid to dissolve the precipitate to prepare colloid.
The acetylacetone is taken as a complexing agent, the zirconium oxychloride is taken as a precursor, and the hydrogen peroxide is taken as a hydrolysis promoter to prepare the zirconium oxide colloid (glass and enamel, 2001 Vol.29 No.4P.41-44), so that the introduction of other inorganic salt impurities can be overcome, and the high-purity sol can be prepared. However, the colloid prepared in this way has poor stability in time, wide particle size distribution and a small amount of micron and particle existence due to the single complexing agent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a precursor sol universal for zirconia ceramic powder. The preparation method has the advantages of less flow, simple process, low requirement on equipment, low cost due to the use of cheap zirconium salt and hydrogen peroxide as raw materials, and easy industrialization.
On the basis of the existing zirconia sol preparation method, the invention takes zirconium oxychloride as a precursor, hydrogen peroxide as a hydrolysis promoter, and strong oxidizing property of the hydrogen peroxide is utilized to reduce chloride ions into chlorine to overflow, so as to obtain colloid with narrow particle size distribution. The zirconium oxychloride is dissolved in a proper amount of mixed liquid of alcohol, water and a proper amount of surfactant which are prepared according to a certain proportion, and the mixed liquid is stirred and mixed evenly. The method selects a proper surfactant and prepares the high-purity, stable and narrow-particle-size-distribution zirconia sol with controllable particle size through a simple process flow. Because other ions and impurities are not introduced in the preparation process, the prepared colloid has high purity, can be used as a precursor sol commonly used in various fields, for example, can be used as a stable sol for electronic materials or coatings, or can be used for preparing nano-grade high-purity powder through drying and washing, and can also be combined with other materials to prepare composite functional ceramic materials. In the preparation process, the whole system is placed in a water area constant temperature environment, and the temperature of the system is stabilized at 20-30 ℃.
According to the invention, the starting material may be zirconium oxychloride or zirconium tetrachloride. When zirconium oxychloride is used, its hydrolysis equation can be expressed as:
the above formula indicates that the generation of hydrogen ions after the hydrolysis of zirconium oxychloride inhibits the further hydrolysis of zirconium oxychloride, and for this reason, we introduce hydrogen peroxide, utilize its strong oxidizing property to oxidize chloride ions, and overflow in the form of chlorine gas, and the reaction equation is as follows:
it is known that the addition of hydrogen peroxide can reduce the concentration of hydrogen ions and promote the hydrolysis. Meanwhile, the size of sol particles is effectively controlled by changing the concentration and the use ratio of hydrogen peroxide, and double charge layers can be formed on the surfaces of the sol particles by using different surfactants, so that stable sol with narrow particle size distribution is obtained.
The technical scheme adopted by the invention is as follows:
a preparation method of zirconia sol is characterized by comprising the following steps: the zirconium salt is zirconium oxychloride or zirconium tetrachloride, the concentration of the hydrogen peroxide is 30-90%, and the preparation method comprises the following steps:
a. calculating the water quantity: selecting proper amount of hydrogen peroxide according to the designed concentration of zirconium sol, calculating the total water amount, and removing H according to the design2O2∶Zr4+The ratio of the water to be introduced into the hydrogen peroxide is calculated, the required water amount is divided into A, B parts for standby application according to the ratio, and the ratio A, B is determined according to the concentration of the prepared solution and the concentration of the hydrogen peroxide;
b. preparing a zirconium oxychloride solution: taking part A of water, adding a proper amount of surfactant, wherein the added amount of the surfactant and Zr4+The molar ratio of the ions is 1: 4-1: 10, and the types of the used surfactants and the proportion of the surfactants are determined according to the concentration of the prepared sol. The surfactant includes: slowly adding zirconium oxychloride into one or more of hydroxypropyl cellulose, citric acid, PEG200, PEG2000, n-butanol and polyacrylamide under vigorous stirring, and continuously stirring for about 30min after completely dissolving;
c. hydrogen peroxide preparation: and mixing part of water in the B part with required hydrogen peroxide, adding one or more of ethylenediamine tetraacetic acid, ethanol, glycol, acetone and acetylacetone, wherein the addition amount of the mixture is 1/2-1/10 of the total volume of the colloid, and uniformly mixing.
d. Putting the zirconium oxychloride solution into a constant-temperature water bath at 20-30 ℃, dropwise adding hydrogen peroxide into the zirconium oxychloride solution at a speed of 0.1-10 ml/min under continuous stirring, continuously stirring for 3-5 h after dropwise adding, sealing and aging.
Compared with the colloid prepared by the previous method, the colloid preparation method of the invention has the following advantages: a precipitator is not needed, and high-purity zirconia sol can be prepared; the process is simple, a special reaction device is not needed, and the reaction temperature is low; by changing H2O2∶Zr4+The sol with different particle sizes can be prepared by adjusting the proportion and the types and the concentration of the surface active agent; the sol with narrow particle size distribution and stability can be prepared by matching different surfactants. The concentration of the sol can be adjusted in a larger range by using hydrogen peroxide with different concentrations. The sol prepared by the invention has strong universality and can be almost used forany ZrO used2Compared with other methods, the colloid prepared by the invention has simple subsequent process required for further preparing high-purity powder or compounding with other materials.
Drawings
FIG. 1 shows different H in examples 1 to 4 of the present invention2O2∶Zr4+Preparation of ZrO in proportions2Schematic of the sol particle size distribution.
Detailed Description
The present invention is described in further detail below.
Example 1
Weighing 10g ZrOCl2·H2O, the molar ratio: zr4+∶H2O28.44g of 35% hydrogen peroxide were weighed out in a ratio of 1: 2.8. Calculated according to the preparation concentration of 0.5mol/L sol, the volume of the final solution is 62ml, the water amount introduced by removing hydrogen peroxide is 7.6ml, 50ml deionized water is measured (a small amount of water is left for final complement), the solution is divided into two parts according to the proportion of A: B being 4: 1, and ZrOCl is dissolved by taking A2·H2O, and adding 2.5ml of a mixed solution of acetone, acetylacetone and PEG200, wherein the volume ratio is as follows: 2: 1. Mixing B with hydrogen peroxide, and adding 2ml ethanol. The mixture was added dropwise at a rate of 0.5ml/min with continuous vigorous stirring. After the dropwise addition, continuously stirring for 3h, complementing the solution amount to 62ml to make the final solution concentration be 0.5mol/l, and then standing and aging for 5-10 h. Preparation of ZrO2The sol particle size distribution is shown in the A region of figure 1.
Example 2
Weighing 10g ZrOCl2·H2O, the molar ratio: zr4+∶H2O212.96g of 35% hydrogen peroxide were weighed out in a ratio of 1: 4.3. Calculated according to the preparation of sol with the concentration of 0.5mol/L, the volume of the final solution is 62ml, the water amount introduced by removing hydrogen peroxide is 11.6ml, 50ml of deionized water is measured, the solution is divided into two parts according to the proportion of A to B being 4 to 1, and the solution A is takenZrOCl decomposition2·H2O, and adding 4.5ml of a mixed solution of acetone, acetylacetone and PEG200, wherein the volume ratio is as follows: 2: 1. Mixing B with hydrogen peroxide and adding 2ml of ethylene glycol. Under continuous and violent stirringThen, the mixture was added dropwise at a rate of 0.3 ml/min. After the dropwise addition, continuously stirring for 3h, complementing the solution amount to 62ml to make the final solution concentration be 0.5mol/l, and then standing and aging for 5-10 h. Preparation of ZrO2The particle size distribution of the sol is shown in the B region of the attached figure 1.
Example 3
Weighing 10g ZrOC12·H2O, the molar ratio: zr4+∶H2O219.59g of 35% hydrogen peroxide were weighed out in a ratio of 1: 6.5. Calculated according to the preparation concentration of 0.5mol/L sol, the volume of the final solution is 62ml, the water amount introduced by removing hydrogen peroxide is 17.9ml, 42ml of deionized water is measured, the solution is divided into two parts according to the proportion of A to B being 3 to 1, and ZrOCl is dissolved in A2·H2O, and adding 5.5ml of a mixed solution of acetone, acetylacetone and PEG200, wherein the volume ratio is as follows: 2: 1. Mixing B withhydrogen peroxide, and adding 2ml ethylene glycol. The mixture was added dropwise at a rate of 0.1ml/min with continuous vigorous stirring. After the dropwise addition, continuously stirring for 3h, complementing the solution amount to 62ml to make the final solution concentration be 0.5mol/l, and then standing and aging for 5-10 h. Preparation of ZrO2The sol particle size distribution is shown in the region C in FIG. 1.
Example 4
Weighing 10g of ZrOCl2·H2O, the molar ratio: zr4+∶H2O227.13g of 35% hydrogen peroxide were weighed out in a ratio of 1: 9. Calculated according to the preparation concentration of 0.5mol/L sol, the volume of the final solution is 62ml, the water amount introduced by removing hydrogen peroxide is 24.41ml, 36ml deionized water is measured, the solution is divided into two parts according to the proportion of A to B being 5 to 1, and ZrOCl is dissolved in A2·H2O, and 6.5ml of a mixed solution of acetone, acetylacetone and PEG200 is added, wherein the volume ratio is as follows: 2: 1. Mixing B with hydrogen peroxide, adding 2ml ethylene glycol, and dropwise adding at 0.1ml/min under continuously and vigorously stirring. After the dropwise addition, continuously stirring for 5h, complementing the solution amount to 62ml to make the final solution concentration be 0.5mol/1, and then standing and aging for 5-10 h. Preparation of ZrO2The particle size distribution of the sol is shown in the D region of the attached figure 1.
Claims (6)
1. A preparation method of zirconia sol is characterized by comprising the following steps: the zirconium salt is zirconium oxychloride or zirconium tetrachloride, the concentration of the hydrogen peroxide is 30-90%, and the preparation method comprises thefollowing steps:
a. calculating the water quantity: selecting proper amount of hydrogen peroxide according to the designed concentration of zirconium sol, calculating the total water amount, and removing H according to the design2O2∶Zr4+The ratio of the water to be introduced into the hydrogen peroxide is calculated, the required water amount is divided into A, B parts for standby application according to the ratio, and the ratio A, B is determined according to the concentration of the prepared solution and the concentration of the hydrogen peroxide;
b. preparing a zirconium oxychloride solution: adding a proper amount of surfactant into the part A of water, slowly adding zirconium oxychloride under vigorous stirring, and continuously stirring for about 30min after the zirconium oxychloride is completely dissolved;
c. hydrogen peroxide preparation: mixing part of water B with hydrogen peroxide, adding one or more of ethylenediamine tetraacetic acid, ethanol, glycol, acetone and acetylacetone, and mixing uniformly;
d. putting the zirconium oxychloride solution into a constant-temperature water bath at 20-30 ℃, dropwise adding hydrogen peroxide into the zirconium oxychloride solution at a speed of 0.1-10 ml/min under continuous stirring, continuously stirring for 3-5 h after dropwise adding, sealing and aging.
2. The method for preparing a zirconia sol according to claim 1, characterized in that: the surfactant is one or more of hydroxypropyl cellulose, citric acid, PEG200, PEG2000, n-butanol, and polyacrylamide.
3. The method for preparing a zirconia sol according to claim 1, characterized in that: the proper amount of hydrogen peroxide is as follows according to a molar ratio: zr4+∶H2O2Calculating according to the ratio of 1: 2-9.
4. The method for preparing a zirconia sol according to claim 1, characterized in that: the ratio of the water amount of the A, B part to the water amount of the B part is 1: 1-5: 1.
5. The method for preparing a zirconia sol according to claim 1, characterized in that: the surfactant and Zr4+The molar ratio of the ions is 1: 4-1: 10.
6. The method for preparing a zirconia sol according to claim 1, characterized in that: the addition amount of one or more mixed liquid of ethylene diamine tetraacetic acid, ethanol, glycol, acetone and acetylacetone is 1/10-1/2 of the total volume of the colloid.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277090A (en) * | 2011-06-20 | 2011-12-14 | 山东大学 | High-temperature inorganic composite adhesive and preparation method thereof |
| CN101311121B (en) * | 2007-05-23 | 2012-07-04 | 日产化学工业株式会社 | Preparation of zirconia sol |
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