CN107987559B - Spherical composite superfine red ceramic pigment and preparation method thereof - Google Patents
Spherical composite superfine red ceramic pigment and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of ceramic pigments, and particularly relates to a preparation method of a composite superfine red ceramic pigment, which comprises the following steps: a certain amount of LaFexEu1‑xO3Adding into the mixed solution (0.12g P)12350ml of absolute ethyl alcohol and 0.4ml of deionized water), and then adding a certain amount of butyl titanate to be uniformly stirred, and dropwise adding ammonia water to adjust the pH value. Stirring at a certain speed, standing for a certain time, collecting the product, and washing with water and absolute ethyl alcohol respectively for three times. Drying, calcining to remove the template, and grinding the product to obtain the red ceramic pigment. The composite superfine red ceramic pigment prepared by the method combines LaFexEu1‑xO3And TiO2The product has the advantages of bright color, high near infrared reflectivity, high chemical stability, etc.
Description
Technical Field
The invention belongs to the technical field of ceramic pigments, and particularly relates to a composite superfine red ceramic pigment and a preparation method thereof.
Background
The red color has a wavelength of about 630-750 nm, is similar to the color of fresh blood, and is one of three primary colors and psychological primary colors. The traditional high near-infrared reflection pigment mainly contains toxic elements such as Pb, Cr and the like, which are harmful to human health and pollute the environment; secondly, most of the light-colored light reflects sunlight to generate 'light pollution'; finally, they are also not very stable and durable, tend to fall off, and have a greatly reduced reflectivity over time. And the traditional pigment with single performance can not meet the requirements of all industries. Meanwhile, when the particle size of the material is reduced to a nanometer level, the material has superior performance which is not compared with the conventional material. Therefore, the method for synthesizing the composite superfine red ceramic pigment with small granularity, good dispersibility, bright color, good stability and high near-infrared reflectivity by using a green energy-saving method has extremely important significance.
TiO2Has high near infrared emissivity and very high reflectivity, but has the defect of easy generation of 'light pollution', so the coating material is not applied much. It is also known from the literature that complex TiO2The coating is significantly better than without TiO2The infrared reflectivity of the coating is high; in addition, the color is seen from the visual effectColor pigments are preferred by people who are darker than white pigments. Therefore, it is important to find a green energy-saving method for synthesizing the functional pigment with small product granularity, high weather resistance, bright color and high near infrared reflectivity.
The patent application with the application number of 201410263554.0 discloses a dark red non-toxic pigment with high near infrared radiation reflectivity and a preparation method thereof, belonging to the technical field of functional pigments. The method adopts a coprecipitation method, the prepared pigment with the function of reflecting infrared radiation has simple equipment required for production, is easy to operate and suitable for large-scale industrial production, and the average spectrum reflectivity in a near-infrared reflection region is more than 68 percent. The pigment prepared by the method does not contain organic solvents, and has the advantages of safety, no toxicity, stable chemical properties, easy long-term storage and the like. The disadvantages are that: the production cost is high, the addition of the precipitator can cause the local concentration to be too high, the agglomeration is generated or the composition is not uniform enough, the calcination temperature is high, and the calcination time is long, so that the energy conservation and emission reduction are not facilitated.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of an inorganic-organic composite superfine red ceramic pigment, which is prepared by mixing active TiO2With the red pigment LaFexEu1-xO3The red environment-friendly inorganic pigment with simple operation and high chemical stability is synthesized at a lower temperature by compounding.
The technical scheme of the invention is as follows:
a preparation method of spherical composite superfine red ceramic pigment comprises the following steps:
1) 0.1g of LaFexEu1-xO3Is added with P123In a mixed solution of absolute ethyl alcohol and deionized water, in the mixed solution, P123The content of (A) is 0.12g, the content of absolute ethyl alcohol is 50ml, and the content of deionized water is 0.4 ml; in the matrix LaFexEu1-xO3In the pigment powder, the mixing amount of Eu is 0-0.2, namely the value range of x is 0.8-1.0; when the mixing amount of Eu is more than 0.2, the color generation of the product is not obviously improved, and the color generation is obviously increased during large-scale productionCost;
2) then adding 0.4ml of butyl titanate, and dropwise adding ammonia water to adjust the pH to 7.0-9.0 when the mixture is uniformly stirred;
3) stirring at the speed of 100-500 r/min, standing for a period of time, collecting products, and washing with water and absolute ethyl alcohol respectively for three times;
4) drying, calcining to remove the template, and grinding the product to obtain the red ceramic pigment.
Further, in the above scheme, the stirring conditions in the step 3) are as follows: stirring for 3-5h at 50-70 ℃; the standing time is 24-48 h.
Preferably, in the above scheme, the pH in step 2) is 8.0, and the pH is adjusted by adding ammonia water dropwise, and it is found through experiments that the pH is difficult to reach 9.0 or more, and the dispersibility and color development of the product are better than those of the other cases when the pH is 8.
Further, in the above scheme, the drying temperature in the step 4) is 70 ℃.
Further, in the above scheme, the calcination conditions in the step 4) are: calcining at 300-500 ℃ for 30 min. When the calcining temperature is lower than 300 ℃, the reaction is insufficient, and the color is impure; when the calcining temperature is higher than 500 ℃, the dispersibility and the color generation of the product are not obviously improved, and if the large-scale production is carried out, the energy consumption is greatly increased, which is not beneficial to energy conservation and emission reduction.
Further, in the above scheme, the LaFe in step 1) isxEu1-xO3Obtained by the following method: firstly, weighing 9g of glycine by a ten-thousandth balance, dissolving the glycine in 150-200 ml of deionized water, stirring the solution on a magnetic stirrer, sequentially adding lanthanum nitrate, ferric nitrate and europium nitrate, stirring the solution for 110 minutes, and adding La (NO)3)3·6H2O、Fe(NO3)3.9H2O、Eu(NO3)3.6H2O is calculated by La, Fe and Eu respectively, and the ratio of glycine: (La + Fe + Eu) molar ratio of 2: 1; heating on a universal electric furnace, rapidly expanding when the liquid is evaporated, releasing gas to generate fluffy powder, namely precursor, calcining and grinding the precursor to obtain the matrix LaFexEu1-xO3A pigment powder.
Further, said added La (NO)3)3·6H2O、Fe(NO3)3.9H2O、Eu(NO3)3.6H2O is respectively: la (NO)3)3·6H2O 8.66g、Fe(NO3)3.9H2O 6.87～7.68g、Eu(NO3)3.6H2O 0.45～1.34g。
Furthermore, the stirring temperature of the magnetic stirrer is 50-70 ℃.
Furthermore, the calcination temperature of the precursor is 700-900 ℃, and the calcination time is 4 h.
Furthermore, the calcination temperature of the precursor is 750-850 ℃. When the calcining temperature is 700-750 ℃ and 850-900 ℃, the dispersibility and the color generation of the product are general; when the calcination temperature is 750-850 ℃, the product has good dispersibility and color generation.
The invention has the beneficial effects that: the invention uses LaFexEu1-xO3Red pigment and TiO2And compounding to form a core-shell structure. TiO 22Has high near infrared reflectivity, but is easy to generate 'light pollution'; LaFexEu1-xO3Is a red pigment, belongs to a perovskite structure and has high chemical stability. Therefore, it is desirable to combine the advantages of the two to achieve a "synergistic effect". The invention aims to synthesize the composite superfine red ceramic pigment with small granularity, high dispersibility, no toxicity or even low toxicity, simple and controllable process, high near-infrared reflectivity, bright color and high chemical stability by adopting an environment-friendly and energy-saving method.
FIG. 1 shows the same amount of doped LaFe0.85Eu0.15O3) X-ray diffraction patterns of the matrix at different calcination temperatures; the temperatures from a to e are 700 ℃, 750 ℃, 800 ℃, 850 ℃ and 900 ℃ respectively;
FIG. 2 is an X-ray diffraction pattern of matrices with different doping amounts at the same calcination temperature (750 ℃); from a to e, x is 1.00, x is 0.95, x is 0.90, x is 0.85, and x is 0.80;
FIG. 3 shows the preferred matrix (LaFe)0.85Eu0.15O3Calcination temperature 750 ℃) is coated with TiO2Front and rear X-ray diffraction patterns;
FIG. 4 shows a preferred substrate (LaFe) magnified 50000 times0.85Eu0.15O3Calcination temperature 750 ℃) is coated with TiO2SEM images of the product before and after;
FIG. 5 is a preferred matrix (LaFe)0.85Eu0.15O3Calcination temperature 750 ℃) is coated with TiO2EDS spot scan of the post product;
FIG. 6 shows the preferred matrix (LaFe)0.85Eu0.15O3Calcination temperature 750 ℃) is coated with TiO2EDS surface scanning of the post product;
FIG. 7 shows the preferred matrix (LaFe) at different magnifications0.85Eu0.15O3Calcination temperature 750 ℃) is coated with TiO2TEM image of the latter product.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
LaFexEu1-xO3Preparation example 1(x ═ 0.95, 750 ℃ C.)
150ml of distilled water are poured into a beaker, the beaker is placed on a magnetic stirrer with the temperature set at 60 ℃ for stirring, 9g of glycine is added, and then 8.66g of La (NO) is added in turn3)3·6H2O, 7.68g Fe (NO)3)3.9H2O, 0.45g of Eu (NO)3)3.6H2And O, stirring for 110 minutes, then putting the mixture into a universal electric furnace for heating, rapidly expanding when the liquid is quickly evaporated, releasing gas to generate fluffy red powder, namely a precursor, and calcining the prepared precursor. Then calcining for 4h at 750 ℃, and grinding to obtain a matrix LaFexEu1-xO3A pigment powder.
LaFexEu1-xO3Preparation example 2(x 0.85, 750 ℃ C.)
Firstly, 180ml of distilled water is poured into a beaker and placed on a magnetic stirrer with the temperature set at 60 DEG CStirring, 9g of glycine are added, followed by 8.66g of La (NO)3)3·6H2O, 6.87g Fe (NO)3)3.9H2O, 1.34g of Eu (NO)3)3.6H2And O, stirring for 110 minutes, then putting the mixture into a universal electric furnace for heating, rapidly expanding when the liquid is quickly evaporated, releasing gas to generate fluffy red powder, namely a precursor, and calcining the prepared precursor. Then calcining for 4h at 750 ℃, and grinding to obtain a matrix LaFexEu1-xO3A pigment powder.
LaFexEu1-xO3Preparation example 3(x ═ 0.85, 700 ℃ C.)
Firstly, 200ml of distilled water is poured into a beaker, the beaker is placed on a magnetic stirrer with the temperature set to be 60 ℃ for stirring, 9g of glycine is added, and then 8.66g of La (NO) is sequentially added3)3·6H2O, 6.87g Fe (NO)3)3.9H2O, 1.34g of Eu (NO)3)3.6H2And O, stirring for 110 minutes, then putting the mixture into a universal electric furnace for heating, rapidly expanding when the liquid is quickly evaporated, releasing gas to generate fluffy red powder, namely a precursor, and calcining the prepared precursor. Then calcined for 4h at 700 ℃, and ground to obtain the matrix LaFexEu1-xO3A pigment powder.
LaFexEu1-xO3Preparation 4(x 0.85, 750 ℃ C.)
Firstly, weighing 9g of glycine by a ten-thousandth balance, dissolving the glycine in 200ml of deionized water, stirring the glycine on a magnetic stirrer at the stirring temperature of 70 ℃, and then sequentially adding lanthanum nitrate, ferric nitrate and europium nitrate and added La (NO)3)3·6H2O、Fe(NO3)3.9H2O、Eu(NO3)3.6H2O is respectively: la (NO)3)3·6H2O 8.66g、Fe(NO3)3.9H2O 6.87g、Eu(NO3)3.6H2O1.34 g, then heating in a universal electric furnace, rapidly expanding when the liquid is evaporated, releasing gas to generate fluffy red powder, namely a precursor, and calcining the prepared precursorCalcining at 750 deg.C for 4 hr, and grinding to obtain matrix LaFexEu1-xO3A pigment powder.
LaFexEu1-xO3Preparation example 5(x ═ 0.85, 800 ℃ C.)
Firstly, weighing 9g of glycine by a ten-thousandth balance, dissolving the glycine in 200ml of deionized water, stirring the glycine on a magnetic stirrer at the stirring temperature of 70 ℃, and then sequentially adding lanthanum nitrate, ferric nitrate and europium nitrate and added La (NO)3)3·6H2O、Fe(NO3)3.9H2O、Eu(NO3)3.6H2O is respectively: la (NO)3)3·6H2O 8.66g、Fe(NO3)3.9H2O 6.87g、Eu(NO3)3.6H2O1.34 g, then heating in a universal electric furnace, rapidly expanding when the liquid is quickly evaporated, releasing gas to generate fluffy red powder, namely a precursor, calcining the prepared precursor at 800 ℃ for 4h, and grinding to obtain a matrix LaFexEu1-xO3A pigment powder.
The substrate (LaFe) obtained in preparation example 1 was added0.95Eu0.05O3Calcination temperature 750 ℃) was used for the preparation of the composite type ultrafine red ceramic pigment of the following example 1:
example 1
A preparation method of a composite superfine red ceramic pigment comprises the following steps:
1) 0.1g of LaFexEu1-xO3Is added into P123In a mixed solution of absolute ethyl alcohol and deionized water, in the mixed solution, P123The content of (A) is 0.12g, the content of absolute ethyl alcohol is 50ml, and the content of deionized water is 0.4 ml;
2) then adding 0.4ml of butyl titanate, and dropwise adding ammonia water to adjust the pH value to 7.0-9.0 when the mixture is uniformly stirred;
3) stirring at the speed of 100r/min, and stirring for 3h at 50 ℃; standing for 24h, collecting the product, and washing with water and absolute ethyl alcohol respectively for three times;
4) drying at 70 ℃, calcining at 300 ℃ for 30min to remove the template, and grinding the product to obtain the red ceramic pigment.
The substrate (LaFe) obtained in preparation example 2 was added0.85Eu0.15O3Calcination temperature 750 ℃) was used for the preparation of the composite type ultrafine red ceramic pigment of the following example 2:
example 2
A preparation method of a composite superfine red ceramic pigment comprises the following steps:
1) 0.1g of LaFexEu1-xO3Is added into P123In a mixed solution of absolute ethyl alcohol and deionized water, in the mixed solution, P123The content of (A) is 0.12g, the content of absolute ethyl alcohol is 50ml, and the content of deionized water is 0.4 ml;
2) then adding 0.4ml of butyl titanate, and dropwise adding ammonia water to adjust the pH value to 8.0 when the mixture is uniformly stirred;
3) stirring at the speed of 300r/min, and stirring for 3h at 50 ℃; standing for 24h, collecting the product, and washing with water and absolute ethyl alcohol respectively for three times;
4) drying at 70 ℃, calcining at 400 ℃ for 30min to remove the template, and grinding the product to obtain the red ceramic pigment.
The substrate (LaFe) obtained in preparation example 3 was added0.85Eu0.15O3Calcination temperature 700 ℃) was used for the preparation of the composite type ultrafine red ceramic pigment of the following example 3:
example 3
A preparation method of a composite superfine red ceramic pigment comprises the following steps:
1) 0.1g of LaFexEu1-xO3Is added into P123In a mixed solution of absolute ethyl alcohol and deionized water, in the mixed solution, P123The content of (A) is 0.12g, the content of absolute ethyl alcohol is 50ml, and the content of deionized water is 0.4 ml;
2) then adding 0.4ml of butyl titanate, and dropwise adding ammonia water to adjust the pH value to 9.0 when the mixture is uniformly stirred;
3) stirring at the speed of 500r/min, and stirring for 3h at 50 ℃; standing for 24h, collecting the product, and washing with water and absolute ethyl alcohol respectively for three times;
4) drying at 70 ℃, calcining at 500 ℃ for 30min to remove the template, and grinding the product to obtain the red ceramic pigment.
The substrate (LaFe) obtained in preparation example 4 was added0.85Eu0.15O3Calcination temperature 750 ℃) was used for the preparation of the composite type ultrafine red ceramic pigment of the following example 4:
a preparation method of a composite superfine red ceramic pigment comprises the following steps:
1) 0.1g of LaFe0.85Eu0.15O3Dissolving in mixed solution (0.12 gP)12350ml of absolute ethyl alcohol and 0.4ml of deionized water);
2) the pH was adjusted to 7 without adding ammonia, then 0.4ml of butyl titanate was added dropwise, stirred at 60 ℃ for 3 h;
3) standing for 24h, collecting the product, and washing with water and absolute ethyl alcohol for 3 times respectively;
4) drying at 70 deg.C;
5) calcining at 400 ℃ for 30min to remove the template to obtain the composite superfine red ceramic pigment.
The substrate (LaFe) obtained in preparation example 5 was added0.85Eu0.15O3Calcination temperature 800 ℃) was used for the preparation of the composite type ultrafine red ceramic pigment of the following example 5:
a preparation method of a composite superfine red ceramic pigment comprises the following steps:
2) 0.1g of LaFe0.85Eu0.15O3Dissolving in mixed solution (0.12 gP)12350ml of absolute ethyl alcohol and 0.4ml of deionized water);
2) dropwise adding a proper amount of ammonia water to make the pH value to be 8, then dropwise adding 0.4ml of butyl titanate, and stirring for 3 hours at the temperature of 60 ℃;
3) standing for 24h, collecting the product, and washing with water and absolute ethyl alcohol for 3 times respectively;
4) drying at 70 deg.C;
5) calcining at 400 ℃ for 30min to remove the template to obtain the composite superfine red ceramic pigment.
XRD test
FIG. 1 shows the same amount of LaFe0.85Eu0.15O3The X-ray diffraction spectra of the matrix at different roasting temperatures, and the comparison of (a) and (b) in figure 1 shows that characteristic peaks are generated at 700 ℃, the crystal forms of the matrix at 700 ℃ and 750 ℃ are basically the same, and the strength of the characteristic peak of the matrix calcined at 750 ℃ is slightly higher than that of the matrix at 700 ℃, and the characteristic peak is sharper. Comparing the 5 graphs in FIG. 1, LaFe at five temperatures can be clearly seen0.85Eu0.15O3The positions of characteristic peaks are the same, the crystal forms are approximately the same, and the peak intensity of the matrix calcined at 750 ℃ is slightly higher than that of the matrix calcined at other temperatures. FIG. 2 is the X-ray diffraction pattern of the matrix with different doping amounts at the same calcination temperature of 750 ℃, from which can be seen LaFeO3The characteristic peak of (A) is sharper, the peak intensity is larger, and the crystallinity is good. When (a) and (b) of FIG. 2 are compared, LaFe is clearly seen0.95Eu0.05O3Peak intensity without LaFeO3Good, but the overall crystal form is unchanged. This is because of doping Eu, resulting in LaFeO3The distortion of the crystal structure results in the decrease of the characteristic peak intensity, but because solid solution is generated after Eu is doped, the crystal structure is not changed, and theta corresponding to each peak on the XRD pattern is the same. As can be seen from (b) and (c) of fig. 2, increasing the Eu content has little effect on the characteristic peaks, and the crystal form is also substantially unchanged. It is understood from the results of (b), (c), (d) and (e) of 2 that the lanthanum ferrite structure is not greatly affected by increasing the amount of Eu to be added, and that the intensity of the characteristic peak is slightly higher when the amount of Eu to be added is 0.15 than when the amount of Eu to be added is other than the amount of La to be added. So that LaFexEu1-xO3(x is 0.15), that is, it is preferable that the amount of Eu added is 0.15. From the above, it is understood that the matrix is preferable when the calcination temperature is 750 ℃ and the Eu content is 0.15.
FIG. 3 shows the preferred matrix (LaFe)0.85Eu0.15O3The X-ray diffraction patterns before and after coating at a calcination temperature of 750 ℃) are shown in the lower part of FIG. 3, and the matrix before coating has a high peak value and good crystallinity; from the upper part of FIG. 3, the coated LaFe is shown0.85Eu0.15O3Is obvious in characteristic peakWeakened, TiO2Becomes the highest peak, indicating that TiO2Have been successfully coated on the outside of the substrate.
SEM test
FIGS. 4(a), (b) are respectively 50000 times larger preferred matrices (750 ℃ calcined LaFe0.85Eu0.15O3) And TiO2SEM images before and after coating. As can be seen from fig. 4(a), the dispersibility of the entire matrix before coating is relatively good, and the matrix is spherical or nearly spherical. As can be seen from fig. 4(b), the coated particles are more round, more spherical particles and better in dispersibility, and the expected effect of spherical shape is basically achieved. As for TiO2The coating situation of (a) is to be further investigated by TEM.
EDS testing
FIG. 5 is a preferred matrix (LaFe)0.85Eu0.15O3Calcination temperature 750 ℃) and TiO2EDS point scan of the coated product, as can be seen from FIG. 5, the sample consists of four elements, O, K, Fe and Eu, and the content of O is higher than that of LaFe0.85Eu0.15O3O content in (C) due to TiO2The coating is coated outside the matrix, so the content of O is improved. Without La this may be encapsulated inside the core shell. See also FIG. 6 for a preferred matrix (LaFe)0.85Eu0.15O3Calcination temperature 750 ℃) and TiO2An EDS surface scanning image of the coated product shows that the sample consists of four elements of La, Eu, O and Fe, and all the elements are uniformly distributed.
TEM test
FIGS. 7(a) and (b) are each a step of calcining 750 ℃ LaFe0.85Eu0.15O3@TiO2The TEM images at pH 8, 40000 and 400000 times, are magnified 40000 times, and it can be seen from the 40000 times magnified image of fig. 7(a) that the particles are uniformly distributed and intact, and the 400000 times magnified image of fig. 7(a) clearly shows the expected effects of round cake shape and dark inside and light outside the color. The color is dark and LaFe calcined at 750 DEG C0.85Eu0.15O3The substrate shell structure is coated with TiO with light peripheral color2Core structure, TiO can be seen2Is uniformly coated on the matrixA surface.
The mechanism of the invention is as follows:
TiO2has high near infrared reflectivity, but is easy to generate 'light pollution' and is made of TiO2The paint system prepared from the light-color pigment of the pigment and filler mostly presents light color and can not meet the color requirement of people. Therefore, the invention provides red perovskite type LaFe with high chemical stabilityxEu1-xO3And TiO with high near infrared reflectivity2In combination, a synergistic effect is achieved. Aims to synthesize the composite superfine red ceramic pigment with small granularity, good dispersibility, low toxicity, no toxicity, high near infrared reflectivity, no light pollution, bright color and good chemical stability by an energy-saving green method.
Claims (1)
1. The preparation method of the spherical composite superfine red ceramic pigment is characterized by comprising the following steps:
1) 0.1g of LaFexEu1-xO3Is added into P123In a mixed solution of absolute ethyl alcohol and deionized water, in the mixed solution, P123The content of (A) is 0.12g, the content of absolute ethyl alcohol is 50ml, and the content of deionized water is 0.4 ml; in the matrix LaFexEu1-xO3In the pigment powder, the mixing amount of Eu is 0.05-0.2, namely the value range of x is 0.8-0.95;
2) then adding 0.4ml of butyl titanate, and dropwise adding ammonia water to adjust the pH to 7.0-9.0 when the mixture is uniformly stirred;
3) stirring at the speed of 100-500 r/min, standing for a period of time, collecting products, and washing with water and absolute ethyl alcohol respectively for three times;
4) drying and calcining to remove the template, and grinding the product to obtain the red ceramic pigment;
the stirring conditions in the step 3) are as follows: stirring for 3-5h at 50-70 ℃; standing for 24-48 h;
the drying temperature in the step 4) is 70 ℃;
the calcining conditions in the step 4) are as follows: calcining for 30min at 300-500 ℃;
the LaFexEu1-xO3 in the step 1) is obtained by the following method: firstly, 9g of glycine is weighed by a ten-thousandth balance and dissolved in 150-200 ml of deionized water, the mixture is stirred on a magnetic stirrer, and then La (NO) is sequentially added3)3·6H2O、Fe(NO3)3.9H2O、Eu(NO3)3.6H2O, stirring for 110 min, La (NO) added3)3·6H2O、Fe(NO3)3.9H2O、Eu(NO3)3.6H2O is calculated by La, Fe and Eu respectively, and the ratio of glycine: (La + Fe + Eu) molar ratio of 2: 1; then heating the mixture on a universal electric furnace, rapidly expanding the mixture when the liquid is quickly evaporated, releasing gas to generate fluffy powder, namely a precursor, calcining and grinding the precursor to obtain a matrix LaFexEu1-xO3A pigment powder;
said added La (NO)3)3·6H2O、Fe(NO3)3.9H2O、Eu(NO3)3.6H2O is respectively: la (NO)3)3·6H2O8.66g、Fe(NO3)3.9H2O 6.87～7.68g、Eu(NO3)3.6H2O 0.45～1.34g；
The stirring temperature on the magnetic stirrer is 50-70 ℃;
the calcination temperature of the precursor is 750-850 ℃, and the calcination time is 4 h.
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