CN100355702C - Method for synthesizing composite oxide powder by non-hydrolytic sol-gel process with alcohol as oxygen donor - Google Patents
Method for synthesizing composite oxide powder by non-hydrolytic sol-gel process with alcohol as oxygen donor Download PDFInfo
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- CN100355702C CN100355702C CNB2006100053165A CN200610005316A CN100355702C CN 100355702 C CN100355702 C CN 100355702C CN B2006100053165 A CNB2006100053165 A CN B2006100053165A CN 200610005316 A CN200610005316 A CN 200610005316A CN 100355702 C CN100355702 C CN 100355702C
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Abstract
The present invention discloses a method for synthesizing composite oxide powder with a nonhydrolytic sol-gel method by using ethanol as an oxygen donor. In the method, an anhydrous metal chloride or an anhydrous bromide and anhydrous low carbon alcohol are used as main raw materials and mixed, the anhydrous metal chloride or the anhydrous bromide and the anhydrous low carbon alcohol react, and obtained sol carries out nonhydrolytic polymerization reaction under the condition of 80 to 160 DEG C and changes into gel; then, the gel is washed and dried, dry gel is obtained, and after being ground, the dry gel is calcined at a low temperature; the composite oxide powder of the present invention is obtained. When the method of the present invention is compared with the existing nonhydrolytic methods using metal alkoxide or ether as an oxygen donor, composite oxides can also be synthetized under a low temperature in the method of the present invention, and the method of the present invention has the advantages of low raw material cost, simple operation, low production cost and industrialized mass production suitability.
Description
Technical field the present invention relates to a kind of synthetic method of composite oxide powder, is specifically related to a kind of method of non-hydrolytic sol-gel process low temperature synthesizing composite oxide powder.
The background technology sol-gel method is one of synthesizing composite oxide powder method commonly used.It is precursor material that the tradition hydrolytic sol-gel process adopts metal alkoxide more, produces hydrolysis, polycondensation in organic medium, makes alkoxide solution be transformed into gel by colloidal sol, and the drying calcination processing obtains composite oxide powder.In hydrolysis, polycondensation process, because the hydrolysis rate difference of different metal alkoxide, its polycondensation product is difficult to reach M-O-M and M '-O-M ' bonding uniform distribution at random, also be difficult to a large amount of M-O-M ' bondings that form, cause the difficult atom level uniform mixing of realizing of each component in the gel, cause the oxide compound synthesis temperature to improve.In addition, the gelation process required time is long, and byproduct of reaction (alcohol and water) is difficult for getting rid of, and causes the production cycle longer.
Hydrolysis reaction does not take place in non-hydrolytic sol-gel process, its only needs to change processing condition just can make that direct condensation forms a large amount of M-O-M ' bondings between the presoma, in gelation process, realize the uniform mixing of each component on the atom level level, greatly reduced the synthesis temperature of composite oxides.Therefore, non-hydrolytic sol-gel process has outstanding advantages such as gel time is short, and byproduct of reaction (haloalkane) is got rid of easily, and with short production cycle and synthesis temperature is low.
According to 247～249 pages of U.S.'s " materials chemistry " (Chemistry of Materials) 1997 9 2292～2299 pages of 11 phases of volume and 13 2 phases of volume of calendar year 2001, the method for existing non-hydrolytic sol-gel process synthesizing composite oxide powder mainly can be divided into two classes:
(1) with metal alkoxide as the oxygen donor synthesizing composite oxide powder, its reaction equation is as follows:
xMX
m+yM(OR)
m+zM′X
n+tM′(OR)
n→
M
(x+y)M′
(z+t)O
(mx/2+my/2+nz/2+nt/2)+2+(mx/2+my/2+nz/2+nt/2)R-X
Mx+nz=my+nt wherein;
(2) adopt various ethers as the oxygen donor synthesizing composite oxide powder, its reaction equation is as follows:
xMX
m+yM′X
n+(mx/2+ny/2)ROR→M
xM′
yO
(mx/2+ny/2)+(mx+ny)R-X
Owing to adopted the very expensive metal alkoxide of price as oxygen donor, not only raw materials cost height, and raw material is difficult for obtaining in the method (1), therefore is difficult to industrialized production; Method (2) adopts various ethers as oxygen donor, has shortcomings such as volatile, easy firing, explosive, and has certain toxicity, working condition is required high, causes the industrial production cost height.
Summary of the invention the object of the present invention is to provide a kind of non-hydrolytic sol-gel process with the alcohol as oxygen donor synthesizing composite oxide powder.The raw material that this method adopted is easy to get, cost is low, has both solved the high problem of cost in the aforesaid method (1), has solved easy firing, explosive in the method (2) again simultaneously, certain toxicity is arranged, and working condition is required problems such as height.
For realizing goal of the invention, a kind of non-hydrolytic sol-gel process of the present invention with the alcohol as oxygen donor synthesizing composite oxide powder, it is characterized in that: with anhydrous metal muriate or bromide is presoma, with the anhydrous low-carbon alcohol is oxygen donor, carry out hybrid reaction by stoichiometric ratio, the colloidal sol of preparing is converted into gel by non-hydrolytic-polymeric reaction under 80～160 ℃ of conditions, through ultrasonic washing, drying, the xerogel of gained carries out low temperature calcination after grinding, can obtain composite oxide powder.
Its reaction equation is as follows:
xMX
m+yM′X
n+(mx/2+ny/2)ROH→
M
xM′
yO
(mx/2+ny/2)+(mx/2+ny/2)R-X+(mx/2+ny/2)HX
Described anhydrous low-carbon alcohol comprises a kind of of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, the trimethyl carbinol, tertiary amyl alcohol, ethylene glycol, glycerol or more than one mixture wherein.
What described ultrasonic washing effect was best is to carry out in dehydrated alcohol or anhydrous isopropyl alcohol;
Described optimum drying temperature is 60～100 ℃;
Described calcining, the ideal calcinating system is: temperature rise rate is 3～5 ℃/min before 400 ℃, rises to required synthesis temperature with 8～10 ℃/min then, insulation 0.5～1h.
It is presoma that the present invention adopts cheap anhydrous metal muriate or bromide, anhydrous low-carbon alcohol is an oxygen donor, by non-hydrolytic sol-gel process low temperature synthesizing composite oxide powder, compare with traditional hydrolytic sol-gel process, present method has been simplified production technique, and in gelation process, realized the uniform mixing of each component on the atom level level, greatly reduce the synthesis temperature of composite oxides; With existing employing metal alkoxide or ether is that the non-hydrolytic sol-gel process of oxygen donor is compared, and has that raw material is cheap, simple to operate, production cost is low, is fit to characteristics such as industrialized production.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 gained powder;
Fig. 2 is the XRD figure spectrum of embodiment 2 gained powders;
Fig. 3 is the XRD figure spectrum of embodiment 3 gained powders;
Fig. 4 is the XRD figure spectrum of embodiment 4 gained powders.
Fig. 5 is a process flow sheet of the present invention
Embodiment
Embodiment 1
With the anhydrous AlCl of 0.036mol
3(analytical pure), 0.018molTiCl
4(chemical pure) is presoma, with 0.091mol anhydrous isopropyl alcohol (C
3H
7OH, analytical pure) the faint yellow vitreosol A of mixed preparing, Sol A is heated to 110 ℃ after, make it in 6h, be converted into gel B, carry out ultrasonic washing 10min with the 0.2mol anhydrous isopropyl alcohol again, place 70 ℃ then in the baking oven drying,, will put into crucible after the xerogel grinding until forming xerogel C, calcine in electric furnace: temperature rise rate is 4 ℃/min before 400 ℃, rise to 750 ℃ with 8 ℃/min then, insulation 30min can obtain aluminium titanates powder (seeing the XRD figure spectrum of Fig. 1).
With the anhydrous AlBr of 0.037mol
3(analytical pure), 0.012molSiCl
4(chemical pure) is presoma, with 0.079mol dehydrated alcohol (C
2H
5OH, analytical pure) preparation Sol A, Sol A is heated to 110 ℃ after, Sol A is converted into gel B in 8h, it is carried out ultrasonic washing 10min with the 0.2mol dehydrated alcohol, and,, will transfer in the crucible after its grinding until forming xerogel C in 70 ℃ of dryings in baking oven, calcine in electric furnace: temperature rise rate is 5 ℃/min before 400 ℃, rise to 900 ℃ with 10 ℃/min then, insulation 60min can obtain mullite powder (seeing the XRD figure spectrum of Fig. 2).
With the anhydrous ZrCl of 0.018mol
4(analytical pure), 0.018molTiCl
4(chemical pure) is presoma, with 0.072mol anhydrous normal butyl alcohol (C
4H
9OH, analytical pure) mixed preparing Sol A, Sol A is heated to 110 ℃ after, make it in 9h, be converted into gel B, carry out ultrasonic washing 10min with the 0.2mol anhydrous isopropyl alcohol again, place 70 ℃ then in the baking oven drying,, will put into crucible after the xerogel grinding until forming xerogel C, calcine in electric furnace: temperature rise rate is 4 ℃/min before 400 ℃, rise to 600 ℃ with 8 ℃/min then, insulation 50min can obtain zirconia titanate powder (seeing the XRD figure spectrum of Fig. 3).
With 0.036molAlCl
3(analytical pure), 0.018molTiCl
4(chemical pure), 0.009molSiCl
4(chemical pure) is presoma, with 0.108mol dehydrated alcohol (C
2H
5The OH analytical pure) preparation Sol A, after Sol A is heated to 110 ℃, Sol A is converted into gel B in 5h, it is carried out ultrasonic washing 10min with the 0.3mol dehydrated alcohol, and dry in baking oven in 70 ℃, until forming xerogel C, to transfer in the crucible after its grinding, calcine in electric furnace: temperature rise rate is 3 ℃/min before 400 ℃, rises to 900 ℃ with 10 ℃/min then, insulation 45min, resultant powder is aluminium titanium silicon ternary oxide---Al through XRD analysis
4Ti
2SiO
12(see figure 4).
Claims (4)
1, the method for a kind of non-hydrolytic sol-gel method synthesizing composite oxide powder with alcohol as oxygen donor, it is characterized in that anhydrous metal muriate or bromide reacting with anhydrous low-carbon alcohol are presoma, with the anhydrous low-carbon alcohol is oxygen donor, by reaction equation
xMX
m+yM′X
n+(mx/2+ny/2)ROH→
M
xM′
yO
(mx/2+ny/2)+(mx/2+ny/2)R-X+(mx/2+ny/2)HX
In stoichiometric ratio carry out hybrid reaction, wherein, described anhydrous low-carbon alcohol is meant a kind of of ethanol, Virahol, propyl carbinol or more than one mixture wherein, the colloidal sol of preparing is converted into gel by non-hydrolytic-polymeric reaction under 80～160 ℃ of conditions, through ultrasonic washing, drying, the xerogel of gained carries out low temperature calcination after grinding, promptly obtain composite oxide powder.
2, the method for synthesizing composite oxide powder according to claim 1 is characterized in that described ultrasonic washing is to carry out in dehydrated alcohol or anhydrous isopropyl alcohol.
3, the method for synthesizing composite oxide powder according to claim 1 is characterized in that described drying temperature is 60～100 ℃.
4, the method for synthesizing composite oxide powder according to claim 1, it is characterized in that described calcining, its calcinating system is: temperature rise rate is 3～5 ℃/min before 400 ℃, rises to required synthesis temperature with 8～10 ℃/min then, insulation 0.5～1h.
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| CN102476819A (en) * | 2010-11-27 | 2012-05-30 | 中国科学院兰州化学物理研究所 | Preparation method of nano alpha-alumina powder |
| CN102432286B (en) * | 2011-09-02 | 2013-07-17 | 景德镇陶瓷学院 | Preparation method of aluminum titanate powder by taking metal aluminum as aluminum source through non-hydrolytic sol-gel process at low temperature |
| 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 |
| CN104556216B (en) * | 2014-12-29 | 2016-05-04 | 景德镇陶瓷学院 | A kind of method that adopts non-hydrolytic sol-gel process to prepare Barium Titanate nano-powder |
| CN105271337B (en) * | 2015-10-21 | 2017-03-08 | 景德镇陶瓷大学 | A kind of method that alumina ultrafine powder body is prepared using non-aqueous depositing technology |
| CN108511797B (en) * | 2018-05-09 | 2022-07-19 | 哈尔滨工业大学（威海） | Li7La3Zr2O12Solid electrolyte preparation method |
| CN109663594A (en) * | 2019-01-23 | 2019-04-23 | 景德镇陶瓷大学 | It is a kind of that MgFe is prepared using non-hydrolytic sol-gel process2O4The method of/C-material and its material obtained |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389939A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院成都有机化学研究所 | Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator |
| CN1618768A (en) * | 2003-11-20 | 2005-05-25 | 华东理工大学 | Improved sol-gel method for preparing nano-powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389939A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院成都有机化学研究所 | Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator |
| CN1618768A (en) * | 2003-11-20 | 2005-05-25 | 华东理工大学 | Improved sol-gel method for preparing nano-powder |
Non-Patent Citations (4)
| Title |
|---|
| Nonhydrolytic Sol-Gel Routes to Oxides.A.Vioux.CHEM.MATER.,Vol.9. 1997 * |
| Transformation of Organsilicon-Loaded Alumina Gel toHomogeneous Aluminosilicates:A Solid-State NMR Study. Dmitry Bravo.Zhivotovskii et al. CHEM.MATER.,Vol.13. 2001 * |
| 溶胶—凝胶工艺在材料科学中的应用 丁星兆等.材料科学与工程，第12卷第2期 1994 * |
| 溶胶—凝胶法制备纳米粉体 姚敏琪等.稀有金属材料与工程，第31卷第5期 2002 * |
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