CN102180516A - Preparation method of non-hydrosol gel of high-dispersibility nano zirconia - Google Patents
Preparation method of non-hydrosol gel of high-dispersibility nano zirconia Download PDFInfo
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- CN102180516A CN102180516A CN 201110061662 CN201110061662A CN102180516A CN 102180516 A CN102180516 A CN 102180516A CN 201110061662 CN201110061662 CN 201110061662 CN 201110061662 A CN201110061662 A CN 201110061662A CN 102180516 A CN102180516 A CN 102180516A
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Abstract
The invention discloses a preparation method of non-hydrosol gel of high-dispersibility nano zirconia. The method comprises the following steps: mixing zirconium salt with an alcohol solvent so as to obtain a precursor; and carrying out low-temperature non-aqueous solvent thermal treatment on the obtained precursor and then carrying out alcohol washing and drying on the obtained product, so as to obtain the high-dispersibility nano zirconia. The high-dispersibility nano zirconia has the advantages of white appearance, no hard agglomeration, small particle size and uniformly distributed particle size, is bulk and can be stably dispersed in water; and a water dispersing liquid can be stably maintained for at least 48 hours without precipitation. The method is simple in synthesis route, is low in reaction temperature and is easy to operate, and the yield can reach 96%, thereby achieving industrial production with low cost on a large scale.
Description
Technical field
Of the present invention to the effect that about a kind of non-aqueous sol-gel preparation method who possesses the nano zircite of polymolecularity.This method is simple to operate, and raw material is easy to get, and the productive rate height in the resulting nano zircite energy disperse water, and can be stablized maintenance for some time.
Background introduction
Zirconia material has high rigidity, high strength, high tenacity, the physical and chemical performance that high wear resistance and chemical resistance or the like are good, at pottery, refractory materials, machinery, electronics, optics, aerospace, biological, the various fields of chemistry or the like obtain to use widely, and the performance of nano zircite is even better, the nano zircite that preparation possesses the high dispersive performance is a difficult problem of needing solution in scientific research and the industrial production badly always, this is because zirconium white is one of important matrix material constituent, if can make the nano zircite that in certain medium, has polymolecularity, the using value of nano zircite is greatly brought into play.
On preparation high dispersion nanometer oxide zirconium, many research work are arranged also at present.Report prepares nano zirconium oxide powder with gas phase hydrolysis method among the CN 1259488A, flood with metal salt solution subsequently, carry out thermolysis again, make the weakly agglomerated nano zirconium oxide powder of surface doping, the Zirconia particles that makes with gas phase hydrolysis method is several nanometers, the tap density of powder is little, and volume density can reach about 1% of tetragonal phase zirconium oxide theoretical density, and it is few to reunite.But this method complicated operation, the energy consumption height, and do not report in the literary composition whether this nano zirconium oxide powder has water dispersible yet.
About the nano zircite of energy stable dispersion in water, report considerably less.Human hydrothermal methods such as Camille G., concrete grammar is, with a certain amount of nitric hydrate oxygen zirconium and six nitric hydrate yttrium water dissolution, add methyl ethyl diketone again, pH with the ammoniacal liquor regulator solution, make pH=7, this mixing solutions is aging at normal temperatures, just can form gel after several weeks, this gel is transferred in the Teflon liner still then, 160 ℃ were reacted 3 hours down, can obtain the stable dispersed nano zirconium white of yttrium, and this mixture is composited by the yttrium oxide of nano zircite and 40%, the powder that obtains after the membrane filtration screening mixes with water after filtration, after ultrasonic 30 minutes, can obtain nano zircite aqueous dispersions [Camille G., the et al. of stable dispersion, Nano single crystals of yttria-stabilized zirconia Cryst.Growth Des., 2009,9,3548-3550].
At present, also there are many research work to be devoted to the surface functionalization of nano zirconia particles, because the zirconium surface avtive spot is many, be easy to be rich in the organic molecule combination of various functional groups with some, therefore can be implemented in various organic solvents, as normal hexane, tetrahydrofuran (THF), stable dispersion in the toluene etc., what have also can be dispersed in the water.The mixture of human zirconium iso-propoxides such as Kai Q.L. and Virahol is the zirconium precursor body, phenylcarbinol is a solvent, solvent thermal reaction is 4 days under 240 ℃ of temperature, obtain the zirconia particles that particle diameter is about 5nm after the reaction, then resulting nano zircite and silane reagent are carried out coupling, after zirconium white after the finishing is dispersed in the organic solvent, can obtain transparent dispersion liquid fully, zirconium white is present in the organic solvent with the form of single particle.Wherein, can stable dispersion [Kai Q.L., et al. Dispersion and functionalization of nonaqueous synthesized zirconia nanocrystals via attachment of in hydrochloric acid soln with the nano zircite that the 3-aminopropyltriethoxywerene werene is modified
In the present invention, it is little that we adopt a kind of non-aqueous sol-gel method simple to operation to prepare particle diameter, and the nano zircite that is evenly distributed, resulting product appearance is white in color, bulk, hard aggregation-free adds this nano zircite in the distilled water, shake gently and get final product stable dispersion in water, need not to carry out the finishing of nanoparticle or in water, add dispersion agent.This method synthetic route is simple, easy handling, and temperature of reaction is low, and productive rate can be realized industrialization production low-costly and in high volume up to 96%.
Summary of the invention
The purpose of this invention is to provide a kind of non-aqueous sol-gel preparation method with nano zirconium oxide powder of polymolecularity, its method is that zirconates is dissolved in the alcoholic solvent, after the presoma process non-aqueous sol-gel thermal treatment that obtains, can obtain possessing the nano zircite of polymolecularity.
The present invention for achieving the above object, the technical scheme of employing is as follows:
The zirconic non-aqueous sol-gel preparation method of a kind of high dispersancy nano is characterized in that, adopts the preparation of low temperature non-aqueous sol-gel method, and preparation process is followed successively by:
Step 1: add zirconates in alcoholic solvent, the amount that is made into zirconates is the presoma of 0.1～1.5 mol;
Step 2: the presoma that obtains in the step 1 is carried out solvent heat treatment, 100～200 ℃ of treatment temps, the time is 6～48 hours;
Step 3: the reaction of step 2 is used the absolute ethanol washing sample after finishing, and product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
The preparation method of high dispersancy nano Zirconium powder of the present invention adopts the preparation of low temperature non-aqueous sol-gel method, and preparation process is followed successively by:
Step 1: add zirconates in alcoholic solvent, the amount that is made into zirconates is the presoma of 0.5～1.2 mol;
Step 2: the presoma that obtains in the step 1 is carried out solvent heat treatment, 100～180 ℃ of treatment temps, the time is 18～36 hours;
Step 3: the reaction of step 2 is used the absolute ethanol washing sample after finishing, and product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Among the preparation method of high dispersion nanometer oxide zirconium powder body of the present invention, described zirconates is zirconium tetrachloride, zirconium oxychloride, Zircosol ZN or zirconium iso-propoxide; Described alcohols is methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, ethylene glycol, propylene glycol or phenylcarbinol.
The invention has the advantages that:
1, adopts non-aqueous sol-gel method simple to operation, can prepare the high dispersion nanometer oxide zirconium;
2, institute's synthetic nano zircite energy stable dispersion is in water;
3, whole process of preparation is simple, and raw material is easy to get, and synthesis temperature is low, need not follow-up heat treatment process, and energy consumption is little, and industrial amplification factor is little, and the productive rate height is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the X-ray powder diffraction of prepared nano zircite
Among the figure: the corresponding zirconium dioxide (JCPDS No.78-1807) of collection of illustrative plates, as can be seen, prepared nano zircite crystallinity is fine from collection of illustrative plates.
Fig. 2 is the photo in kind of the nano zircite aqueous dispersions of different concns
Among the figure: the 1-mass percent concentration is the initial photo of 0.1% nano zircite aqueous dispersions, the 2-mass percent concentration is the initial photo of 1% nano zircite aqueous dispersions, the 3-mass percent concentration is 0.1% the photo of nano zircite aqueous dispersions after 48 hours, and the 4-mass percent concentration is 1% the photo of nano zircite aqueous dispersions after 48 hours.From photo as can be seen, this aqueous dispersions can be stablized maintenance at least 48 hours, and sedimentation does not take place.Utilize Zetasizer Nano particle-size analyzer to test its Zeta potential, concentration is that the Zeta potential of the nano zircite aqueous dispersions of 0.1% and 1% (mass percent concentration) is respectively 37.4 millivolts and 34.5 millivolts, the absolute value of its Zeta potential shows that all greater than 30 millivolts nano zircite energy stable dispersion is in water.
Embodiment
The preparation of low temperature non-aqueous sol-gel method is adopted in the zirconic non-aqueous sol-gel preparation of high dispersancy nano, and preparation process is followed successively by:
Step 1: in methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, ethylene glycol, propylene glycol or phenylcarbinol solvent, add zirconates zirconium tetrachloride, zirconium oxychloride, Zircosol ZN or zirconium iso-propoxide, the amount that is made into zirconates is the presoma of 0.1～1.5 mol;
Step 2: the presoma that obtains in the step 1 is carried out solvent heat treatment, 100～200 ℃ of treatment temps, the time is 6～48 hours;
Step 3: the reaction of step 2 is used the absolute ethanol washing sample after finishing, and product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 2
The preparation of low temperature non-aqueous sol-gel method is adopted in the zirconic non-aqueous sol-gel preparation of high dispersancy nano, and preparation process is followed successively by:
Step 1: in methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, ethylene glycol, propylene glycol or phenylcarbinol solvent, add zirconates zirconium tetrachloride, zirconium oxychloride, Zircosol ZN or zirconium iso-propoxide, the amount that is made into zirconates is the presoma of 0.5～1.2 mol;
Step 2: the presoma that obtains in the step 1 is carried out solvent heat treatment, 100～180 ℃ of treatment temps, the time is 18～36 hours;
Step 3: the reaction of step 2 is used the absolute ethanol washing sample after finishing, and product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 3
The preparation of high dispersancy nano Zirconium powder, preparation process is followed successively by:
Step 1: add zirconium tetrachloride in phenylcarbinol, the amount that is made into zirconium tetrachloride is the presoma of 0.5 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 180 ℃, and the time is 20 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 4
The preparation of high dispersancy nano Zirconium powder, preparation process is followed successively by:
Step 1: add zirconium oxychloride in ethanol, the amount that is made into zirconium oxychloride is the presoma of 1.0 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 180 ℃, and the time is 20 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 5
The preparation of high dispersancy nano Zirconium powder, preparation process is:
Step 1: add zirconium iso-propoxide in ethanol, the amount that is made into zirconium iso-propoxide is the presoma of 0.6 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 180 ℃, and the time is 20 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 6
The preparation of high dispersancy nano Zirconium powder, preparation process is:
Step 1: add zirconium tetrachloride in ethanol, the amount that is made into zirconium tetrachloride is the presoma of 0.8 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 120 ℃, and the time is 24 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 7
The preparation of high dispersancy nano Zirconium powder, preparation process is:
Step 1: add zirconium iso-propoxide in ethylene glycol, the amount that is made into zirconium iso-propoxide is the presoma of 1.0 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 150 ℃, and the time is 18 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 8
The preparation of high dispersancy nano Zirconium powder, preparation process is:
Step 1: add zirconium tetrachloride in methyl alcohol, the amount that is made into zirconium tetrachloride is the presoma of 1.2 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 100 ℃, and the time is 24 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 9
The preparation of high dispersancy nano Zirconium powder, preparation process is:
Step 1: add zirconium tetrachloride in Virahol, the amount that is made into zirconium tetrachloride is the presoma of 1.0 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 150 ℃, and the time is 24 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Embodiment 10
The nano zirconium oxide powder preparation of polymolecularity, preparation process is:
Step 1: add Zircosol ZN in propyl carbinol, the amount that is made into Zircosol ZN is the presoma of 0.5 mol;
Step 2: the presoma of step 1 is carried out solvent heat treatment, and treatment temp is 150 ℃, and the time is 36 hours;
Step 3: centrifugal after step 2 finishes, and the product usefulness washing with alcohol that will centrifugally obtain 3 times, product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
Claims (3)
1. the zirconic non-aqueous sol-gel preparation method of high dispersancy nano is characterized in that, adopts the preparation of low temperature non-aqueous sol-gel method, and preparation process is followed successively by:
Step 1: add zirconates in alcoholic solvent, the amount that is made into zirconates is 0.1～1.5 mol presoma;
Step 2: the presoma that obtains in the step 1 is carried out solvent heat treatment, 100～200 ℃ of treatment temps, the time is 6～48 hours;
Step 3: the reaction of step 2 is used the absolute ethanol washing sample after finishing, and product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
2. the zirconic non-aqueous sol-gel preparation method of high dispersancy nano according to claim 1 is characterized in that, adopts the preparation of low temperature non-aqueous sol-gel method, and preparation process is followed successively by:
Step 1: add zirconates in alcoholic solvent, the amount that is made into zirconates is 0.5～1.2 mol presoma;
Step 2: the presoma that obtains in the step 1 is carried out solvent heat treatment, 100～180 ℃ of treatment temps, the time is 18～36 hours;
Step 3: the reaction of step 2 is used the absolute ethanol washing sample after finishing, and product promptly obtains possessing the nano zirconium oxide powder of polymolecularity 50 ℃ of air dryings 12 hours.
3. the zirconic non-aqueous sol-gel preparation method of high dispersancy nano according to claim 1 and 2 is characterized in that described zirconates is zirconium tetrachloride, zirconium oxychloride, Zircosol ZN, or zirconium iso-propoxide; Described alcohols is methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, ethylene glycol, propylene glycol or phenylcarbinol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765936A (en) * | 2012-08-17 | 2012-11-07 | 景德镇陶瓷学院 | Stable zirconium oxide superfine power prepared by adopting non-aqueous solvent process and preparation method thereof |
| CN103373743A (en) * | 2013-07-12 | 2013-10-30 | 南京宇热材料科技有限公司 | Polyol assisted hydrothermal method for synthesis of zirconium oxide nano-powder |
| CN107055608A (en) * | 2016-10-21 | 2017-08-18 | 华南农业大学 | A kind of transparent dispersion liquid of nano zirconium dioxide and preparation method and application |
| CN112028626A (en) * | 2020-08-03 | 2020-12-04 | 山东金三河新材料科技有限公司 | Preparation method of zirconia bioactive ceramic |
| CN115321488A (en) * | 2022-06-30 | 2022-11-11 | 苏州大学 | Method for preparing self-dispersed nano metal oxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164899A (en) * | 2007-09-29 | 2008-04-23 | 中国科学院山西煤炭化学研究所 | Method for synthesizing non-aqueous system nano-crystal zirconium dioxide |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164899A (en) * | 2007-09-29 | 2008-04-23 | 中国科学院山西煤炭化学研究所 | Method for synthesizing non-aqueous system nano-crystal zirconium dioxide |
Non-Patent Citations (3)
| Title |
|---|
| 《无机盐工业》 20060228 蒋银花等 溶胶-凝胶法制备钇掺杂的纳米氧化锆粉体 29-35 第38卷, 第2期 * |
| 《材料科学与工程学报》 20081031 李广慧等 溶剂热法制备氧化锆纳米粉体及其发光性能 724-727 第26卷, 第5期 * |
| 《物理化学学报》 20081231 李为臻等 溶剂热法合成纯单斜和四方晶相氧化锆中的溶剂效应 2172-2178 第24卷, 第12期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765936A (en) * | 2012-08-17 | 2012-11-07 | 景德镇陶瓷学院 | Stable zirconium oxide superfine power prepared by adopting non-aqueous solvent process and preparation method thereof |
| CN102765936B (en) * | 2012-08-17 | 2013-11-06 | 景德镇陶瓷学院 | Stable zirconium oxide superfine power prepared by adopting non-aqueous solvent process and preparation method thereof |
| CN103373743A (en) * | 2013-07-12 | 2013-10-30 | 南京宇热材料科技有限公司 | Polyol assisted hydrothermal method for synthesis of zirconium oxide nano-powder |
| CN107055608A (en) * | 2016-10-21 | 2017-08-18 | 华南农业大学 | A kind of transparent dispersion liquid of nano zirconium dioxide and preparation method and application |
| CN112028626A (en) * | 2020-08-03 | 2020-12-04 | 山东金三河新材料科技有限公司 | Preparation method of zirconia bioactive ceramic |
| CN115321488A (en) * | 2022-06-30 | 2022-11-11 | 苏州大学 | Method for preparing self-dispersed nano metal oxide |
| CN115321488B (en) * | 2022-06-30 | 2023-10-27 | 苏州大学 | Method for preparing self-dispersion nano metal oxide |
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