CN103922354A - High-yield zirconium silicate powder synthesized by sol-gel method - Google Patents
High-yield zirconium silicate powder synthesized by sol-gel method Download PDFInfo
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- CN103922354A CN103922354A CN201410167366.8A CN201410167366A CN103922354A CN 103922354 A CN103922354 A CN 103922354A CN 201410167366 A CN201410167366 A CN 201410167366A CN 103922354 A CN103922354 A CN 103922354A
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- zirconium
- sol
- zirconium silicate
- tetraethoxy
- ethanol
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Abstract
The invention provides high-yield zirconium silicate powder synthesized by a sol-gel method. According to a preparation method of the zirconium silicate power, zirconium oxychloride and ethyl orthosilicate are used as raw materials, ferric nitrate is used as a catalyst, and water and ethanol are added for serving as solvents. The preparation method comprises the following steps: mixing a certain amount of ethyl orthosilicate with water and ethanol at a certain ratio, and then hydrolyzing under an alkaline condition; after regulating the pH of the solution to 7, adding water solutions of zirconium oxychloride and ferric nitrate, hydrolyzing under an alkaline condition to obtain a precursor sol; then performing treatment processes such as refluxing and drying on the sol so as to obtain zirconium silicate dried gel; and finally smashing and incinerating the dried gel, thereby obtaining the zirconium silicate powder. Compared with an existing sol-gel method, the preparation method has the advantages of lower zirconium silicate powder synthesis temperature, high yield, simple process and convenience in operation.
Description
Technical field
The present invention relates to a kind of method of sol-gel method synthetic silicic acid zirconium powder body.
Background technology
Zirconium silicate is the main component of zircon, has the performance of many uniquenesses.As Heat stability is good, thermal conductivity is low, thermal expansivity is little, and its intensity is also unattenuated at the high temperature of 1400 ℃, sintering zirconium silicate has than mullite and the better thermal shock resistance of zirconium white simultaneously, and these performances make zirconium silicate become the important candidate material of high-temperature structural ceramics.Yet the zirconium silicate that occurring in nature exists contains a lot of impurity conventionally, and purity is lower, and zirconium silicate can be decomposed at low temperatures.Therefore,, for high temperature application, synthetic high-purity zirconium silicate powder just seems extremely important.Key in herein background technology and describe paragraph.
At present, the method for preparing zirconium silicate powder mainly contains solid reaction process, the precipitator method, hydrothermal method and sol-gel method etc.Wherein, solid phase method synthesis temperature is high, and the zirconium silicate powder purity of preparation is low, particle diameter is large; Precipitator method particle diameter is wider, dispersed poor, easily introduces foreign ion; Hydrothermal method requires harsh to conversion unit, operation easier is large, is difficult to large-scale industrial production; Sol-gel method is one of study hotspot of current synthetic silicic acid zirconium powder body.
In the research of preparing zirconium silicate, Curtis C. E. etc. [C.E.Curtis, H.G.Sowman. Journal of the American ceramic society, 1993,36,190.] are with ZrO
2and SiO
2for raw material is prepared zirconium silicate with solid phase method, 1315 ℃ start to form ZrSiO
4, at 1500 ℃, productive rate reaches 85%; Takao Itoh etc. [Takao Itoh. Cryst Growth, 1992,125,223.] be take zirconium oxychloride silicon sol and 1200 ℃ of calcinings, are started to form zircon as raw material adopts the precipitator method; Du Chunsheng etc. [Du Chunsheng, Ge Zhiping, Yang Zhengfang, Yuan Qiming, Chen Yuru. silicate journal, 1999,27,346.] adopt sol-gel method, add crystal seed, 1100 ℃ of calcinings, start there is ZrSiO
4generate, during to 1200 ℃, synthetic ratio is 40%.Dong Xueliang [Zeng Chongsheng, appoints snow Tan for Dong Xueliang, Teng Yuancheng. Chinese powder technology, 2010,16,4] etc. by sol-gel method, prepare zirconium silicate, by adding crystal seed, synthesis temperature is reduced to 1200 ℃.W.P.C.M. Alahakoon[W.P.C.M. Alahakoon, S.E. Burrows, A.P, Howes, B.S.B. Karunaratne, M.E. Smith, R. Dobedor. Journal of the European Ceramic Society, 2010,30,2515.] etc. studied the impact that Fe, Al are prepared zircon, result shows that Fe can promote ZrSiO
4crystallization, Al can promote densification.
Summary of the invention
The method that the object of this invention is to provide simple, the easy control of a kind of technique, low-cost synthetic silicic acid zirconium powder body.
For achieving the above object, the technical solution used in the present invention, it is characterized in that: take zirconium oxychloride, tetraethoxy is raw material, take iron nitrate as catalyzer, add water and ethanol as solvent, by sol-gel method, obtain zirconium silicate xerogel, then, through pulverizing, calcining, obtain zirconium silicate powder.
In such scheme, first a certain amount of tetraethoxy is mixed according to a certain percentage with water, ethanol, under alkaline condition, be hydrolyzed; Then pH value of solution is adjusted to 7, adds afterwards the aqueous solution of zirconium oxychloride and iron nitrate, under alkaline condition, hydrolysis obtains precursor sol.
In such scheme, the tetraethoxy of optimization and water, proportion of ethanol are by volume: tetraethoxy: water: ethanol=1:3 ~ 6:3 ~ 6.
In such scheme, the concentration of the zirconium oxychloride of optimization is 0.1 ~ 1molL
-1.
In such scheme, the tetraethoxy of optimization, zirconium oxychloride, iron nitrate ratio are in molar ratio: tetraethoxy: zirconium oxychloride: iron nitrate=1:0.1 ~ 1:0.01 ~ 0.08.
In such scheme, the hydrolysis temperature of optimization is 30 ~ 70 ℃, and the calcinating system of optimization is: 800 ~ 1500 ℃ of insulation 1 ~ 6h, temperature rise rate: 2 ~ 10 ℃ of min
-1.
The present invention adopts sol-gel method to prepare zirconium silicate powder, and the temperature of its synthetic silicic acid zirconium powder body is 800 ~ 1500 ℃, compares with existing synthetic technology, synthesis temperature reduces, and technique is simple, convenient operation, and reaction time is short, temperature is low, reproducible, is applicable to suitability for industrialized production.
Accompanying drawing explanation
The XRD figure spectrum of Fig. 1 embodiment 1, wherein X-coordinate is 2 θ angles, and ordinate zou is diffraction peak intensity, and unit is a.u.;
The XRD figure spectrum of Fig. 2 embodiment 2, wherein X-coordinate is 2 θ angles, and ordinate zou is diffraction peak intensity, and unit is a.u.;
The XRD figure spectrum of Fig. 3 embodiment 3, wherein X-coordinate is 2 θ angles, and ordinate zou is diffraction peak intensity, and unit is a.u.;
Fig. 4 is the SEM image of embodiment 1;
Fig. 5 is process flow sheet of the present invention.
specific implementation method
Embodiment 1
Zirconium oxychloride (ZrOCl
28H
2o), tetraethoxy (Si (OC
2h
5)
4), iron nitrate (Fe (NO
3)
3), ammoniacal liquor, dehydrated alcohol and hydrochloric acid is analytical pure.In reaction vessel, add Si (OC
2h
5)
4solution, then to add successively distilled water and dehydrated alcohol, their volume ratio be V (Si (OC
2h
5)
4): V (H
2o): V (C
2h
5oH)=1:4:6.Reaction vessel is placed on magnetic stirring apparatus and keeps 50 ℃ of thermostatically heating constantly stirring, dropwise add ammoniacal liquor to Si (OC
2h
5)
4fully hydrolysis produces a large amount of flosss, then slowly drips hydrochloric acid soln and regulates pH=7.By concentration, be 0.7 mol/L ZrOCl
28H
2o and Fe (NO
3)
3mixing solutions add in reaction vessel and fully mix, amount of substance is than being n (ZrOCl
28H
2o): n (Si (OC
2h
5)
4): n (Fe (NO
3)
3)=1:1:0.06, dropwise splashes into ammoniacal liquor to ZrOCl
28H
2o is fully hydrolyzed generation colloidal sol, and colloidal sol is dried at 70 ℃ and formed xerogel in loft drier, finally xerogel is pulverized to calcining.Its calcinating system is: temperature rise rate: 5 ℃ of min
-1, at 1200 ℃, be incubated 4h, synthetic ratio 91.20%, synthetic zirconium silicate powder is shown in accompanying drawing 1.
Embodiment 2
Zirconium oxychloride (ZrOCl
28H
2o), tetraethoxy (Si (OC
2h
5)
4), iron nitrate (Fe (NO
3)
3), ammoniacal liquor, dehydrated alcohol and hydrochloric acid is analytical pure.The preparation of xerogel is identical with embodiment 1.But its calcinating system is: temperature rise rate: 5 ℃ of min
-1, at 1300 ℃, be incubated 4h, synthetic ratio 92.31%, synthetic zirconium silicate powder is shown in accompanying drawing 2.
Embodiment 3
Zirconium oxychloride (ZrOCl
28H
2o), tetraethoxy (Si (OC
2h
5)
4), iron nitrate (Fe (NO
3)
3), ammoniacal liquor, dehydrated alcohol and hydrochloric acid is analytical pure.The preparation of xerogel is identical with embodiment 1.But its calcinating system is: temperature rise rate: 5 ℃ of min
-1, at 1400 ℃, be incubated 4h, synthetic ratio 91.68%, synthetic zirconium silicate powder is shown in accompanying drawing 3.
Claims (6)
1. the method for a sol-gel method synthetic silicic acid zirconium powder body, it is characterized in that: take zirconium oxychloride, tetraethoxy is raw material, take iron nitrate as catalyzer, add water and ethanol as solvent, by sol-gel method, obtain zirconium silicate xerogel, then through pulverizing, calcining, obtain zirconium silicate powder.
2. the method for synthetic silicic acid zirconium according to claim 1, is characterized in that: first a certain amount of tetraethoxy is mixed according to a certain percentage with water, ethanol, under alkaline condition, be hydrolyzed; Then pH value of solution is adjusted to 7, adds afterwards the aqueous solution of zirconium oxychloride and iron nitrate, under alkaline condition, hydrolysis obtains precursor sol.
3. the method for synthetic silicic acid zirconium according to claim 1, is characterized in that: the ratio of tetraethoxy and water, ethanol is by volume: tetraethoxy: water: ethanol=1:3 ~ 6:3 ~ 6.
4. the method for synthetic silicic acid zirconium according to claim 1, is characterized in that: the concentration of zirconium oxychloride is 0.1 ~ 1molL-1.
5. the method for synthetic silicic acid zirconium according to claim 1, is characterized in that: the ratio of tetraethoxy, zirconium oxychloride, iron nitrate is in molar ratio: tetraethoxy: zirconium oxychloride: iron nitrate=1:0.1 ~ 1:0.01 ~ 0.08.
6. the method for synthetic silicic acid zirconium according to claim 1, is characterized in that: calcination condition is: 800 ~ 1500 ℃ of temperature, insulation 1 ~ 6h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108706597A (en) * | 2018-06-12 | 2018-10-26 | 湖北大学 | A kind of zirconium silicate powder and the preparation method and application thereof |
| CN109809820A (en) * | 2019-01-28 | 2019-05-28 | 江西嘉捷信达新材料科技有限公司 | Zirconium carbide, nanometer silicon carbide composite fibre enhancing silicon carbide fibre and preparation method thereof |
| CN110075820A (en) * | 2019-04-25 | 2019-08-02 | 陕西科技大学 | A kind of Al2O3/ZrO2/SiO2Composite visible light catalyst and preparation method thereof |
| CN114057477A (en) * | 2021-11-19 | 2022-02-18 | 广州世陶新材料有限公司 | Porous zirconium silicate prepared by dry method and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250480A (en) * | 1990-03-16 | 1993-10-05 | Tosoh Corporation | Method for preparing zircon powder |
| CN102557055A (en) * | 2011-11-23 | 2012-07-11 | 陕西科技大学 | Preparation method of zirconium silicate powder |
| CN103588211A (en) * | 2013-11-12 | 2014-02-19 | 北京理工大学 | Preparation method of spherical zirconium silicate nano aggregate powder |
-
2014
- 2014-04-24 CN CN201410167366.8A patent/CN103922354A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250480A (en) * | 1990-03-16 | 1993-10-05 | Tosoh Corporation | Method for preparing zircon powder |
| CN102557055A (en) * | 2011-11-23 | 2012-07-11 | 陕西科技大学 | Preparation method of zirconium silicate powder |
| CN103588211A (en) * | 2013-11-12 | 2014-02-19 | 北京理工大学 | Preparation method of spherical zirconium silicate nano aggregate powder |
Non-Patent Citations (4)
| Title |
|---|
| ALAHAKOON ET AL.: "Fully densified zircon co-doped with iron and aluminium prepared by sol–gel processing，W.P.C.M", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| GIUSEPPE CAPPELLETTI ET AL.: "The influence of iron content on the promotion of the zircon structure and the optical properties of pink coral pigments", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| P. TARTAJ ET AL.: "Iron Zircon Pigments Prepared by Pyrolysis of Aerosols", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
| 董雪亮等: "溶胶-凝胶法合成硅酸锆", 《中国粉体技术》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108706597A (en) * | 2018-06-12 | 2018-10-26 | 湖北大学 | A kind of zirconium silicate powder and the preparation method and application thereof |
| CN109809820A (en) * | 2019-01-28 | 2019-05-28 | 江西嘉捷信达新材料科技有限公司 | Zirconium carbide, nanometer silicon carbide composite fibre enhancing silicon carbide fibre and preparation method thereof |
| CN109809820B (en) * | 2019-01-28 | 2021-11-02 | 江西嘉捷信达新材料科技有限公司 | Zirconium carbide and silicon carbide nano composite fiber reinforced silicon carbide fiber and preparation method thereof |
| CN110075820A (en) * | 2019-04-25 | 2019-08-02 | 陕西科技大学 | A kind of Al2O3/ZrO2/SiO2Composite visible light catalyst and preparation method thereof |
| CN114057477A (en) * | 2021-11-19 | 2022-02-18 | 广州世陶新材料有限公司 | Porous zirconium silicate prepared by dry method and preparation method thereof |
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Application publication date: 20140716 |