CN113371756B - La-Sc-ZrO2 nano crystal material and preparation method thereof - Google Patents
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Abstract
The invention discloses a La-Sc-ZrO 2 Nanocrystalline material and preparation method thereof, belonging to inorganic nonmetallic material, la-Sc-ZrO 2 The nano crystal material is prepared by taking zirconia as a main body, wherein part of Zr ions in zirconia crystal lattice are replaced by La ions and Sc ions. The preparation method comprises the following steps: a. la is subjected to 2 O 3 、Sc 2 O 3 And ZrOCl 2 ·H 2 O is dissolved in hydrochloric acid solution, and then ethanol water solution is added to obtain a reaction system; b. NaOC is introduced into 2 H 5 Dissolving in water to obtain NaOC 2 H 5 A solution; c. the reaction system obtained in the step a and NaOC are reacted 2 H 5 Uniformly mixing the solutions, and heating by microwaves to obtain a reaction initial product; d. centrifugally separating the initial reaction product, washing the solid with water and alcohol repeatedly until the washing liquid is free of Cl ‑ Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material. The invention prepares La-Sc-ZrO 2 The nano crystal has simple process, short period, good dispersivity and stable performance.
Description
Technical Field
The invention relates to the field of inorganic nonmetallic materials, in particular to a La-Sc-ZrO 2 Nanocrystalline materials and methods of making the same.
Background
Zirconium dioxide is an inorganic nonmetallic material with high melting point, high boiling point, small heat conductivity coefficient, large thermal expansion coefficient, good wear resistance and excellent corrosion resistance, and is mainly applied to solid oxide fuel cells, thermal barrier coating materials, catalyst carriers,Lubricating oil additives, medical use, gas sensitivity, abrasion resistant materials, jewel industry, piezoelectric elements and the like have been widely used and developed. With the development of high-precision and high-reliability electronic components, high-purity and high-purity stable ZrO is required in the electronic ceramic and fine ceramic manufacturing industries 2 。
The stability of zirconium dioxide is related to its crystalline form, zirconium dioxide has 3 crystalline forms and belongs to the polycrystalline phase-converted oxide. The stable low temperature phase is monoclinic (m-ZrO) 2 ) Tetragonal phase (t-ZrO 2) at above 1000 DEG C 2 ) Gradually forming until 2370 ℃ only tetragonal phase exists, and cubic phase (c-ZrO 2) is obtained above 2370 ℃ to melting point 2 ）。ZrO 2 During heating up, the volume shrinks, while during cooling down, the volume expands. Therefore, in order to prevent the volume change during use, it is necessary to perform a crystal form stabilization treatment.
There are many methods for synthesizing zirconium dioxide in common use, such as: the zirconia crystal prepared by the sol-gel method has uniform components and large specific surface area, but the production cost is high due to the introduction of organic reagents such as complexing agents and the like; the coprecipitation method has simple process, but impurities are easy to introduce, the formed precipitate is in a colloid state, and is difficult to filter and clean, and caking is easy to occur during drying and dehydration; the zirconium oxide crystal prepared by the laser method has small particle size, uniform distribution and less agglomeration, but has high requirements on equipment; compared with the above method, the microwave method is a rapid, simple, power-saving and agglomeration-avoiding heating method. The microwave heating is the heating of the material body caused by dielectric loss in an electromagnetic field, has the characteristics of being fast and sufficient, enabling the heated object to be the heated object, not needing heat conduction, being capable of preparing superfine powder, solving the technical problem of agglomeration caused by traditional heating, simultaneously preparing the nano crystal with more complete crystal, finer granularity and more stability, and having the advantages of short preparation period, simple preparation process, energy saving, environmental protection, automatic operation realization and the like.
Therefore, how to increase the temperature range in which zirconium dioxide exists stably in a cubic crystal phase, and to obtain zirconium dioxide nano crystal particles with good dispersibility and uniform particle size is a problem to be solved.
Disclosure of Invention
The invention relates to a La-Sc-ZrO 2 Nanocrystalline materials, and methods of preparing La-Sc-ZrO using microwave heating are also provided 2 A method of nanocrystalline material.
Based on the above purpose, the invention adopts the following technical scheme:
La-Sc-ZrO 2 The nano crystal material is prepared from zirconia as main body, wherein part of Zr ions in the zirconia lattice are replaced by La and Sc ions, wherein La 3+ 、Sc 3+ Ion-substituted part Zr 4+ Into the zirconia lattice to form stable La-Sc-ZrO 2 Nanocrystalline materials promote the transformation of the metastable tetragonal phase of the crystal into a cubic phase without the formation of a stable phase monoclinic phase.
La-Sc-ZrO as described above 2 The nanocrystalline material consists of a lanthanum stabilizer, a scandium stabilizer and ZrOCl 2 ·H 2 O is made into lanthanum stabilizer, scandium stabilizer is ZrOCl 2 ·H 2 The molar ratio of O is (0.5-1): 5-8): 85-92.
Preferably, the lanthanum stabilizer is La 2 O 3 The scandium stabilizer is Sc 2 O 3 。
The application also provides a La-Sc-ZrO 2 A method of preparing a nanocrystalline material comprising the steps of:
a. la is subjected to 2 O 3 、Sc 2 O 3 And ZrOCl 2 ·H 2 O is dissolved in hydrochloric acid solution, and then ethanol water solution is added to obtain a reaction system;
b. NaOC is introduced into 2 H 5 Dissolving in water to obtain NaOC 2 H 5 A solution;
c. the reaction system obtained in the step a and NaOC are reacted 2 H 5 Uniformly mixing the solutions, and heating by microwaves to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, washing the solid with water and alcohol repeatedly until the washing liquid is free of Cl - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Further, the method comprises the steps of,in step a, the La 2 O 3 : Sc 2 O 3 :ZrOCl 2 The molar ratio of H2O was (0.5-1): 5-8): 85-92, and the concentration of the solid dispersion of the resulting mixed solution system was 0.4mol/L.
Further, in the step a, the concentration of the hydrochloric acid solution is 4mol/L; naOC in step b 2 H 5 The concentration of the solution is 1mol/L, and the reaction system obtained in the step a and NaOC 2 H 5 The volume ratio of the solutions was 1:1.
Further, the microwave heating temperature is 140-200 ℃ and the time is 2-15min.
La-Sc-ZrO obtained by the above method 2 The nanocrystalline material has uniformly dispersed crystal grains and uniform granularity.
La-Sc-ZrO obtained by the above method 2 The nano crystal material is widely used in the fields of refractory brick manufacture, crucible manufacture, high-frequency ceramics, grinding materials, ceramic pigment manufacture, zirconate manufacture and the like, and is especially suitable for high temperature conditions.
The invention has the beneficial effects that:
(1) According to the invention, ethanol is selected as a solvent and a dispersing agent of reactants, sodium ethoxide is selected as a precipitating agent, and under the combined action of ethanol and sodium ethoxide, the dispersibility of the zirconium dioxide product is better, and the prepared zirconium dioxide nanocrystals are finer and more uniform in granularity.
(2) The microwave heating is the heating of the material body caused by dielectric loss in an electromagnetic field, has the characteristics of being fast and sufficient, enabling the heated object to be the heated object, and not needing heat conduction. Meanwhile, the preparation method provided by the application is short in period and small in occupied area of microwave heating, so that high environmental temperature is avoided, and the labor condition of workers is greatly improved.
(3) The invention is prepared by doping La 3+ 、Sc 3+ Ions, La 3+ 、Sc 3+ Doping of ions does not cause ZrO 2 The crystal is severely distorted mainly due to part of La 3+ 、Sc 3+ Ion-substituted Zr 4+ In the presence of ZrO 2 Oxygen defects in the crystal, la-Sc-ZrO 2 The oxygen vacancies between La, sc and Zr are increased, and the larger atomic weight difference and ionic radius difference between La, sc and Zr lead to ZrO 2 The structure and the performance of the crystal are more stable, the metastable tetragonal phase of the crystal is promoted to be converted into a cubic phase, no stable phase monoclinic phase is generated, and La-Sc-ZrO of the cubic phase crystal form 2 The crystal structure can still keep good stability at high temperature of 1500 ℃.
(4) According to the invention, ethanol and sodium ethoxide are respectively used as dispersing and precipitating agents, zirconium ions and ethanol ions react to generate a composite tetrahedron structure, and the tetrahedron structures are aggregated and connected to generate a net structure. As microwave heating is rapid, the precipitation in the heating process can rapidly destroy the network structure, thereby forming zirconium dioxide nanocrystals, having better dispersibility and solving the problem of nanocrystal agglomeration.
Drawings
FIG. 1 is an XRD pattern of the product obtained in example 4 by calcination for 6 hours at 160℃for 10min under microwave heating
FIG. 2 is an XRD pattern of the product obtained in example 5 by calcination for 6 hours at 160℃for 15min
FIG. 3 is an XRD pattern of the product obtained in example 6 by calcination for 6 hours at 170℃for 10min
FIG. 4 is an SEM image of the product obtained in example 4 by calcination for 6 hours at 160℃for 10min
FIG. 5 is an SEM image of the product obtained by calcining example 6 at 170℃for 10 min.
Detailed Description
The present application is described in detail with reference to examples.
Comparative example 1 (common oven heating)
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weigh 0.052 La 2 O 3 Sc 0.358g 2 O 3 、9.936g ZrOCl 2 ·H 2 O is respectively dissolved in 4mol/L hydrochloric acid solution, namely La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 0.5:8:91.5, then ethanol and deionized water are added, the volume ratio of the ethanol to the deionized water is 1:1, and the concentration of metal ions in the mixed system is 0.4mol/L;
b. weighing 1.361g NaOC 2 H 5 Dissolving in deionized water to obtain NaOC with concentration of 1mol/L 2 H 5 Is an aqueous solution of (a);
c. combining the system obtained in step a with NaOC in step b 2 H 5 According to 1:1, transferring the mixture into an autoclave, and heating the mixture in a common oven at 160 ℃ for 24 hours to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, and repeatedly washing the solid with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Example 1
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weigh 0.052 La 2 O 3 Sc 0.358g 2 O 3 9.936g ZrOCl 2 ·H 2 O is respectively dissolved in 4mol/L hydrochloric acid solution, namely La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 0.5:8:91.5, then ethanol and deionized water are added, the volume ratio of the ethanol to the deionized water is 1:1, and the concentration of metal ions in the mixed system is 0.4mol/L;
b. weighing 1.361g NaOC 2 H 5 Dissolving in deionized water to obtain NaOC with concentration of 1mol/L 2 H 5 A solution;
c. the system obtained in step a and step b is prepared according to the following formula 1: mixing uniformly in a volume ratio of 1, transferring into an autoclave, and heating in a microwave instrument at 160 ℃ for 5min to obtain a reaction initial product;
d. centrifuging the reaction initial product, taking solid and removingRepeatedly washing with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Example 2
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weighing La of 0.073 2 O 3 Sc 0.358g 2 O 3 9.414g ZrOCl 2 ·H 2 O is respectively dissolved in 4mol/L hydrochloric acid solution, namely La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 0.7:8:91.3, then ethanol and deionized water are added, the volume ratio of the ethanol to the deionized water is 1:1, and the concentration of metal ions in the mixed system is 0.4mol/L;
b. weighing 1.361g NaOC 2 H 5 Dissolving in deionized water to obtain NaOC with concentration of 1mol/L 2 H 5 A solution;
c. the system obtained in step a and step b is prepared according to the following formula 1:1, transferring the mixture into an autoclave, and heating the mixture in a microwave instrument at 160 ℃ for 5min to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, and repeatedly washing the solid with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Example 3
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weigh 0.104 La 2 O 3 Sc 0.358g 2 O 3 9.384g ZrOCl 2 ·H 2 O is respectively dissolved in 4mol/L hydrochloric acid solution, namely La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 1:8:91, then ethanol and deionized water are added, the volume ratio of the ethanol to the deionized water is 1:1, and the concentration of metal ions in the mixed system is 0.4mol/L;
b. weighing 1.361g NaOC 2 H 5 Is dissolved inIn deionized water, naOC with the concentration of 1mol/L is obtained 2 H 5 A solution;
c. the system obtained in step a and step b is prepared according to the following formula 1:1, transferring the mixture into an autoclave, and heating the mixture in a microwave instrument at 160 ℃ for 5min to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, and repeatedly washing the solid with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Example 4
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weigh 0.052 La 2 O 3 Sc 0.358g 2 O 3 9.936g ZrOCl 2 ·H 2 O is respectively dissolved in 4mol/L hydrochloric acid solution, namely La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 0.5:8:91.5, then ethanol and deionized water are added, the volume ratio of the ethanol to the deionized water is 1:1, and the concentration of metal ions in the mixed system is 0.4mol/L;
b. weighing 1.361g NaOC 2 H 5 Dissolving in deionized water to obtain NaOC with concentration of 1mol/L 2 H 5 A solution;
c. the system obtained in step a and step b is prepared according to the following formula 1:1, transferring the mixture into an autoclave, and heating the mixture in a microwave instrument at 160 ℃ for 10min to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, and repeatedly washing the solid with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Example 5
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weigh 0.052 La 2 O 3 Sc 0.358g 2 O 3 9.936g ZrOCl 2 ·H 2 O is respectively dissolved in 4mol/L saltAcid solution, i.e. La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 0.5:8:91.5, then ethanol and deionized water are added, the volume ratio of the ethanol to the deionized water is 1:1, and the concentration of metal ions in the mixed system is 0.4mol/L;
b. weighing 1.361g NaOC 2 H 5 Dissolving in deionized water to obtain NaOC with concentration of 1mol/L 2 H 5 A solution;
c. the system obtained in step a and step b is prepared according to the following formula 1:1, transferring the mixture into an autoclave, and heating the mixture in a microwave instrument at 160 ℃ for 15min to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, and repeatedly washing the solid with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Example 6
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weigh 0.052 La 2 O 3 Sc 0.358g 2 O 3 9.936g ZrOCl 2 ·H 2 O is respectively dissolved in 4mol/L hydrochloric acid solution, namely La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 0.5:8:91.5, then ethanol and deionized water are added, the volume ratio of the ethanol to the deionized water is 1:1, and the concentration of metal ions in the mixed system is 0.4mol/L;
b. weighing 1.361g NaOC 2 H 5 Dissolving in deionized water to obtain NaOC with concentration of 1mol/L 2 H 5 A solution;
c. the system obtained in step a and step b is prepared according to the following formula 1:1, transferring the mixture into an autoclave, and heating the mixture in a microwave instrument at 170 ℃ for 10min to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, and repeatedly washing the solid with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 Nanometer scaleCrystalline material.
Comparative example 2 (no NaOC added) 2 H 5 ）
La-Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. weigh 0.052 La 2 O 3 Sc 0.358g 2 O 3 9.936g ZrOCl 2 ·H 2 O is dissolved in 5mL of hydrochloric acid solution with concentration of 4mol/L respectively, based on complete dissolution, wherein La 2 O 3 :Sc 2 O 3 :ZrOCl 2 ·H 2 The mol percentage of O is 0.5:8:91.5, 10mL of ethanol and deionized water are respectively added, and the mixture is uniformly mixed to obtain the concentration of solid substances of 0.4mol/L;
b. adding deionized water with the same volume into the mixed solution in the step a, mixing and stirring uniformly, transferring into an autoclave, and heating in a microwave instrument at 160 ℃ for 5min to obtain a reaction initial product;
c. centrifugally separating the initial reaction product, and repeatedly washing the solid with deionized water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Comparative example 3 (La was not added) 2 O 3 Stabilizing agent
Sc-ZrO 2 A nanocrystalline material, the method of making comprising the steps of:
a. 0.358g of Sc was weighed out as required 2 O 3 9.936g ZrOCl 2 ·H 2 O is dissolved in 5mL of hydrochloric acid solution with the concentration of 4mol/L, 10mL of ethanol and deionized water are respectively added and uniformly mixed until the O is completely dissolved;
b. weighing 1.361g NaOC 2 H 5 Dissolving in deionized water to obtain NaOC with concentration of 1mol/L 2 H 5 A solution;
c. the system obtained in step a and step b is prepared according to the following formula 1:1, transferring the mixture into an autoclave, and heating the mixture in a microwave instrument at 160 ℃ for 5min to obtain a reaction initial product;
d. centrifuging the reaction initial product, taking solid and deionizedRepeatedly washing with water and ethanol until no Cl exists - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
Performance analysis
1. Particle size detection
The particle size distributions of comparative examples 1 to 3 and examples 1 to 6 were tested, and the specific results are shown in Table 1.
As can be seen from Table 1, the size of the nanocrystals was the largest with the non-sodium ethoxide as the precipitant, the average size was 125nm, the sizes were larger when the non-microwave heating and lanthanum-free stabilizer was added, the sizes of the nanocrystals were smaller when the lanthanum stabilizer was added and microwave heating was performed, and the sizes were smaller the higher the microwave heating temperature and the longer the heating time, the smaller the sizes were, and the particles were more uniform.
2. XRD and SEM measurements
The nanocrystalline materials prepared in the above comparative examples and examples were sampled in a certain amount, and after heating in a muffle furnace at 600 ℃ for 2 hours, XRD and SEM measurements were performed, and the test results are shown in FIGS. 1 to 5.
FIG. 1 is an XRD pattern for a nanocrystalline material prepared in example 4 under heating at 160deg.C for 10min, with the characteristic diffraction peak of scandium oxide at 31.4℃in FIG. 1, illustrating Sc under these conditions 3+ The ions did not completely enter the zirconia crystals, but the XRD pattern of the nanocrystalline material prepared in example 6 under heating at 170℃for 10min, the XRD pattern of the nanocrystalline material prepared in example 5 under heating at 160℃for 15min, and the characteristic diffraction peaks of the cubic phase only in both FIG. 3 and FIG. 2, indicate that ZrO can be obtained with appropriate increase of the heating time and increase of the reaction temperature 2 Oxygen defects in the crystal, la 3+ 、Sc 3+ Substituted part Zr 4+ Generating cubic La-Sc-ZrO with more stable crystal forms 2 Crystals, zrO 2 The structure and performance of the crystal are more stable.
FIG. 5 is an SEM image of example 6 calcined for 6 hours at 170deg.C for 10min, with an average particle size of 30nm and a uniform particle distribution, and FIG. 4 is an SEM image of example 4 calcined for 6 hours at 160deg.C for 10min, with an average particle size of 39nm, and it can be seen that the dispersibility and particle regularity of FIG. 4 are not as good as those of FIG. 5.
Claims (4)
1. La-Sc-ZrO 2 Nanocrystalline material, characterized by being composed of a lanthanum stabilizer, scandium stabilizer and ZrOCl 2 ·H 2 O is prepared, zirconium oxide is taken as a main body, part of Zr ions in a zirconium oxide crystal lattice are replaced by La ions and Sc ions, and the crystal is in a cubic phase structure;
the lanthanum stabilizer, scandium stabilizer and ZrOCl 2 ·H 2 The mol ratio of O is (0.5-1): 5-8): 85-92;
the lanthanum stabilizer is La 2 O 3 The scandium stabilizer is Sc 2 O 3 ；
The La-Sc-ZrO 2 A method of preparing a nanocrystalline material comprising the steps of:
a. la is subjected to 2 O 3 、Sc 2 O 3 And ZrOCl 2 ·H 2 O is dissolved in hydrochloric acid solution, and then ethanol water solution is added to obtain a reaction system;
b. NaOC is introduced into 2 H 5 Dissolving in water to obtain NaOC 2 H 5 A solution;
c. the reaction system obtained in the step a and NaOC are reacted 2 H 5 Uniformly mixing the solutions, and heating by microwaves to obtain a reaction initial product;
d. centrifugally separating the initial reaction product, washing the solid with water and alcohol repeatedly until the washing liquid is free of Cl - Then drying at 80 ℃ to obtain La-Sc-ZrO 2 A nanocrystalline material.
2. A La-Sc-ZrO as claimed in claim 1 2 A nanocrystalline material characterized by: in the step a, the concentration of metal ions in the mixed solution system is 0.4mol/L.
3.A La-Sc-ZrO as defined in claim 1 or 2 2 A nanocrystalline material characterized by: in the step a, the concentration of the hydrochloric acid solution is 4mol/L; naOC in step b 2 H 5 The concentration of the solution is 1mol/L, and the reaction system obtained in the step a and NaOC 2 H 5 The volume ratio of the solutions was 1:1.
4. A La-Sc-ZrO as claimed in claim 1 2 A nanocrystalline material characterized by: the microwave heating temperature is 140-200deg.C, and the time is 2-15min.
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