CN111646506B - Method for preparing nano zirconium oxide by internal gel method - Google Patents
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- CN111646506B CN111646506B CN202010704273.XA CN202010704273A CN111646506B CN 111646506 B CN111646506 B CN 111646506B CN 202010704273 A CN202010704273 A CN 202010704273A CN 111646506 B CN111646506 B CN 111646506B
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- 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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Abstract
The invention belongs to the technical field of material science, and particularly relates to a method for preparing nano zirconia by an internal gel method; the method comprises the steps of curing a zirconium source and a urea solution in situ through chemical gel, continuously heating until the urea is decomposed, converting the colloid into a precursor of zirconium oxide, drying the colloid, calcining at 800 ℃ for 4 hours, and obtaining the high-quality composite nano zirconium oxide, wherein the reaction is uniform reaction, and the nucleation particle size is uniform, so that the composite nano zirconium oxide powder with uniform size and good dispersibility is obtained.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a method for preparing nano zirconium oxide by an internal gel method.
Background
The nanometer zirconia powder is beneficial to realizing the optimization of the performance of zirconia ceramics, and the preparation of the nanometer zirconia powder is always a hotspot of research. The manufacture of high-performance ceramic materials has high requirements on the used powder, and has strict requirements on the shape and size of particles in the powder besides accurate and uniform requirements on the chemical composition and phase composition of the powder and low impurity content. Roughly summarized as follows:
1) The particle size is small;
2) The particle size distribution range is narrow;
3) The shape of the particles is preferably spherical or equiaxed;
4) No agglomeration or small agglomeration degree between the particles.
The preparation method of the nano zirconia powder mainly comprises a solid phase method, a wet chemical method (a precipitation method, a sol-gel method, a hydrothermal method and an emulsion method), a chemical vapor phase method and the like, the zirconia powder prepared by the existing preparation method has the problem of easy agglomeration, and how to eliminate the agglomeration of the nano zirconia powder by simplifying the steps is a technical problem which needs to be solved urgently.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a method for preparing nano zirconia by an inner gel method, which simplifies the operation steps and eliminates the agglomeration of nano zirconia powder.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing nano zirconia by an inner gel process comprises the following steps:
step 1: mixing a soluble zirconium source and a soluble yttrium source, mixing the mixture with deionized water to prepare a solution A with the concentration of 0.5-2.0mol/L, wherein the total weight of the zirconium source and the yttrium source is M1, and adding urea into the solution A by weighing the urea according to the molar ratio of 1: 1.1 of zirconium to urea to obtain a solution B;
and 2, step: weighing acrylamide with the weight of M2 and N, N' -methylene bisacrylamide with the weight of M3, and putting into the solution A for dissolving to obtain a solution C, wherein the ratio of M2 to M1 is 1: 4-1: 3, and the ratio of M3 to M2 is 1: 30-1: 15;
and step 3: adding ammonium persulfate and tetramethyl ethylenediamine into the solution C, and uniformly stirring to obtain a solution D;
and 4, step 4: heating the solution D to complete gelation, taking out and cutting the solution D into small gel blocks;
and 5: soaking the small gel blocks in distilled water, cleaning and filtering, repeating for multiple times until the filtrate contains less than 20ppm of chloride ions Korean material, and finally cleaning with anhydrous ethanol once and filtering to obtain colloidal particles; drying the colloidal particles at 90-110 ℃;
and 6: and calcining the dried particles at 800 ℃ for 4 hours to obtain the nano zirconia powder.
The invention has the beneficial effects that: in the method for preparing the nano zirconia by the internal gel process, a zirconium source and a urea solution are cured in situ through chemical gel, the chemical gel is continuously heated until the urea is decomposed, the colloid is converted into a precursor of the zirconia, the colloid is dried and then calcined for 4 hours at 800 ℃, and the high-quality composite nano zirconia can be obtained.
Drawings
Fig. 1 is an X-ray diffraction analysis spectrum of nano zirconia prepared by a method for preparing nano zirconia by an internal gelation process according to an embodiment of the present invention.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The most key concept of the invention is as follows: the chemical gel is used for solidifying the zirconium source and the urea solution in situ, the heating is continuously carried out until the urea is decomposed, the colloid is converted into a precursor of the zirconia, and the colloid is dried and then calcined for 4 hours at 800 ℃, so that the high-quality composite nano zirconia can be obtained.
The invention provides a method for preparing nano zirconia by an inner gel process, which comprises the following steps:
step 1: mixing a soluble zirconium source and a soluble yttrium source, mixing the mixture with deionized water to prepare a solution A with the concentration of 0.5-2.0mol/L, wherein the total weight of the zirconium source and the yttrium source is M1, and adding urea into the solution A by weighing the urea according to the molar ratio of 1: 1.1 of zirconium to urea to obtain a solution B;
and 2, step: weighing acrylamide with the weight of M2 and N, N' -methylene bisacrylamide with the weight of M3, and putting into the solution A for dissolving to obtain a solution C, wherein the ratio of M2 to M1 is 1: 4-1: 3, and the ratio of M3 to M2 is 1: 30-1: 15;
and step 3: adding ammonium persulfate and tetramethyl ethylenediamine into the solution C, and uniformly stirring to obtain a solution D;
and 4, step 4: heating the solution D to complete gelation, taking out and cutting the solution D into small gel blocks;
and 5: soaking the small gel blocks in distilled water, cleaning and filtering, repeating for multiple times until the filtrate contains less than 20ppm of chloride ions Korean material, and finally cleaning with anhydrous ethanol once and filtering to obtain colloidal particles; drying the colloidal particles at 90-110 ℃;
step 6: and calcining the dried particles at 800 ℃ for 4 hours to obtain the nano zirconia powder.
In the method for preparing the nano zirconia by the internal gel process, a zirconium source and a urea solution are cured in situ through chemical gel, the chemical gel is continuously heated until the urea is decomposed, the colloid is converted into a precursor of the zirconia, the colloid is dried and calcined at 800 ℃ for 4 hours, and the high-quality composite nano zirconia can be obtained, the reaction is uniform, the nucleation granularity is uniform, and therefore the composite nano zirconia powder with uniform size and good dispersibility is obtained.
Further, in the method for preparing the nano zirconia by the internal gel process, the molar ratio of the ammonium persulfate to the zirconium is 1: 25.
Furthermore, in the method for preparing nano-zirconia by the internal gel process, the molar ratio of the tetramethylethylenediamine to the zirconium is 13: 500.
Further, in the method for preparing the nano zirconia by the inner gel process, the soluble yttrium source is any one or two of yttrium chloride, yttrium oxalate, yttrium nitrate and yttrium acetate.
Further, in the method for preparing the nano-zirconia by the internal gel process, the soluble zirconium source is any one or two of zirconium oxychloride and zirconium acetate.
Further, in the method for preparing nano zirconia by the internal gel process, the molar ratio of the zirconium element to the yttrium element in the reaction solution A is 97: 6.
Further, in the method for preparing nano zirconia by the internal gel process, the soluble yttrium source is yttrium nitrate hexahydrate.
Further, in the method for preparing nano-zirconia by the internal gel process, the soluble zirconium source is zirconium oxychloride containing crystal water.
Further, in the method for preparing nano zirconia by using the internal gel process, the step 4 is specifically: heating the solution D to 80 ℃, waiting for 30min, taking out the solution D after complete gelation, and cutting the solution D into small gel blocks with the width of 0.5 mm.
Example 1
Weighing 171.2g of zirconium oxychloride (containing crystal water) and 11.85g of yttrium nitrate hexahydrate according to the proportion of 3Y, and dissolving in 250ml of deionized water; weighing 33g of urea and dissolving the urea in the zirconium solution; 70g of organic monomers were weighed: acrylamide, and 3g of a crosslinking agent: dissolving N, N' -methylene-bisacrylamide into the mixed solution; adding 5g of ammonium persulfate and 2ml of tetramethylethylenediamine into the solution, stirring uniformly, heating to 80 ℃, waiting for 30min, taking out after the ammonium persulfate and the tetramethylethylenediamine are completely gelled, and cutting into small squares of about 0.5 mm; soaking the small gel blocks in distilled water, cleaning and filtering repeatedly until the content of chloride ions in filtrate is less than 20ppm, and filtering and drying the colloid particles (at 90-110 ℃); calcining the dried colloid at the high temperature of 800 ℃ for 4 hours to obtain nano zirconia powder with good dispersibility; the specific surface area of the powder was 6.463m as measured by a specific surface area meter 2 The crystal phase is t (c) phase, and the primary particle size is less than or equal to 30nm.
Example 2
171.2g of zirconium oxychloride (containing crystal water) and 5.2g of magnesium chloride are weighed and dissolved in 250ml of deionized water; weighing 33g of urea and dissolving the urea in the zirconium solution; 70g of organic monomer are weighed: acrylamide, and 3g of a crosslinking agent: dissolving N, N' -methylene bisacrylamide into the mixed solution; adding 5g of ammonium persulfate and 2ml of tetramethylethylenediamine into the solution, stirring uniformly, heating to 80 ℃, waiting for 30min, taking out after the ammonium persulfate and the tetramethylethylenediamine are completely gelled, and cutting into small squares of about 0.5 mm; soaking the small gel blocks in distilled water, cleaning and filtering repeatedly until the content of chloride ions in filtrate is less than 20ppm, and filtering and drying the colloidal particles (at 90-110 ℃); calcining the dried colloid at the high temperature of 800 ℃ for 4 hours to obtain nano zirconia powder with good dispersibility; the specific surface area of the powder is 7.356m measured by a specific surface area meter 2 The crystal phase is t (c) phase, and the primary particle size is less than or equal to 30nm.
Example 3
A method for preparing nano zirconia by an inner gel process is characterized by comprising the following steps:
step 1: mixing a soluble zirconium source and a soluble yttrium source, mixing the mixture with deionized water to prepare a solution A with the concentration of 0.5-2.0mol/L, wherein the total weight of the zirconium source and the yttrium source is M1, and adding urea into the solution A by weighing the urea and the zirconium source in a molar ratio of 1: 1.1 to obtain a solution B; the soluble yttrium source is any one or two of yttrium chloride, yttrium oxalate, yttrium nitrate and yttrium acetate; the soluble zirconium source is one or two of zirconium oxychloride and zirconium acetate; the molar ratio of the zirconium element to the yttrium element in the reaction solution A is 97: 6;
step 2: weighing acrylamide with the weight of M2 and N, N' -methylene bisacrylamide with the weight of M3, and putting into the solution A for dissolving to obtain a solution C, wherein the ratio of M2 to M1 is 1: 4-1: 3, and the ratio of M3 to M2 is 1: 30-1: 15;
and step 3: adding ammonium persulfate and tetramethylethylenediamine into the solution C, and uniformly stirring to obtain a solution D; the molar ratio of the tetramethylethylenediamine to the zirconium is 13: 500;
and 4, step 4: heating the solution D to 80 ℃, waiting for 30min, taking out and cutting the solution D into small gel blocks with the width of 0.5mm after complete gelation; the molar ratio of the ammonium persulfate to the zirconium is 1: 25;
and 5: soaking the small gel blocks in distilled water, cleaning and filtering, repeating for multiple times until the filtrate contains less than 20ppm of chloride ions Korean material, and finally cleaning with anhydrous ethanol once and filtering to obtain colloidal particles; drying the colloidal particles at 90-110 ℃;
step 6: and calcining the dried particles at 800 ℃ for 4 hours to obtain the nano zirconia powder.
In summary, in the method for preparing nano-zirconia by the internal gel process provided by the invention, a zirconium source and a urea solution are cured in situ by chemical gel, and are continuously heated until the urea is decomposed, so that the colloid is converted into a precursor of the zirconia, the colloid is dried and then is calcined at 800 ℃ for 4 hours, and then the high-quality composite nano-zirconia can be obtained, the reaction is uniform, the nucleation particle size is uniform, and thus the composite nano-zirconia powder with uniform size and good dispersibility is obtained.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (10)
1. A method for preparing nano zirconia by an inner gel process is characterized by comprising the following steps:
step 1: mixing a soluble zirconium source and a soluble yttrium source, mixing the mixture with deionized water to prepare a solution A with the concentration of 0.5-2.0mol/L, wherein the total weight of the zirconium source and the yttrium source is M1, and adding urea into the solution A by weighing the urea according to the molar ratio of 1: 1.1 of zirconium to urea to obtain a solution B;
and 2, step: weighing acrylamide with the weight of M2 and N, N' -methylene bisacrylamide with the weight of M3, and putting into the solution B for dissolving to obtain a solution C, wherein the ratio of M2 to M1 is 1: 4-1: 3, and the ratio of M3 to M2 is 1: 30-1: 15;
and 3, step 3: adding ammonium persulfate and tetramethylethylenediamine into the solution C, and uniformly stirring to obtain a solution D;
and 4, step 4: heating the solution D to complete gelation, taking out and cutting the solution D into small gel blocks;
and 5: soaking the small gel blocks in distilled water, cleaning and filtering, repeating for multiple times until the filtrate contains less than 20ppm of chloride ions Korean material, and finally cleaning with anhydrous ethanol once and filtering to obtain colloidal particles; drying the colloidal particles at 90-110 ℃;
step 6: and calcining the dried particles at 800 ℃ for 4 hours to obtain the nano zirconia powder.
2. The method for preparing nano zirconia by the internal gel process according to claim 1, wherein the molar ratio of the ammonium persulfate to the zirconium is 1: 25.
3. The method for preparing nano zirconia by the inner gel process as claimed in claim 1, wherein the molar ratio of the tetramethylethylenediamine to the zirconium is 13: 500.
4. The method for preparing nano zirconia by the inner gel process according to claim 1, wherein the soluble yttrium source is any one or two of yttrium chloride, yttrium oxalate, yttrium nitrate and yttrium acetate.
5. The method for preparing nano zirconia by the inner gel process according to claim 1, wherein the soluble zirconium source is one or two of zirconium oxychloride and zirconium acetate.
6. The method for preparing nano zirconia by the inner gel process according to claim 1, wherein the molar ratio of the zirconium element to the yttrium element in the solution A is 97: 6.
7. The method for preparing nano zirconia by the inner gel process according to claim 1, wherein the soluble yttrium source is yttrium nitrate hexahydrate.
8. The method for preparing nano zirconia by the inner gel process according to claim 1, wherein the soluble zirconium source is zirconium oxychloride containing crystal water.
9. The method for preparing nano zirconia by the inner gel process according to claim 1, wherein the step 4 is specifically as follows: heating the solution D to 80 ℃, waiting for 30min, taking out the solution D after complete gelation, and cutting the solution D into small gel blocks with the width of 0.5 mm.
10. A nano zirconia obtained by the method for preparing nano zirconia by the inner gel process according to any one of claims 1 to 9.
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