Monodisperse spherical particle dysprosium oxide with particle size of less than 300nm and preparation method of monodisperse spherical particle dysprosium oxide

Abstract

The invention relates to the technical field of spherical particle dysprosium oxide, and discloses monodisperse spherical particle dysprosium oxide with the particle size smaller than 300 nm and a preparation method of the monodisperse spherical particle dysprosium oxide. The preparation method comprises the following steps: S1, a precipitate preparation process: a, preparing a dysprosium chloride-PEG mixed solution; preparing a urea solution; b, adding the dysprosium chloride-PEG mixed solution into a urea solution to obtain a primary material A mixed solution; c, heating the primary material A mixed solution in an electric furnace, keeping the temperature constant, and adjusting the pH value to obtain a precipitate A; d, aging the precipitate, discarding mother liquor, washing, and carrying out suction filtration to obtain a precipitate B; s2, a calcining process: a, putting the precipitate into a crucible, and opening a cover; b, putting the crucible into a muffle furnace for calcining, and calcining in three stages in a stepped temperature control manner; and S3, an ultrasonic process. Realizing lt; successful research and development of 300nm submicron particle rare earth dysprosium oxide not only is a size breakthrough, but also monodispersity means that the particles are highly uniform in size, morphology and composition, and the rare earth dysprosium oxide has good application prospects in the fields of catalysis, biomedicine, magnetic materials and the like.

Description

Technical Field

[0001] This invention relates to the field of spherical dysprosium oxide technology, specifically to a monodisperse spherical dysprosium oxide particle with a particle size of less than 300 nm and its preparation method. Background Technology

[0002] In today's era, technological innovation has become the core engine driving social progress. The preparation and application research of monodisperse (PDI < 0.3, often considered "monodisperse" in industry), spherical, submicron-sized (100-1000 nm) dysprosium oxide (Dy₂O₃) has become an important topic in materials science, nanotechnology, and rare earth functional materials in recent years. Its research background and technological development are mainly driven by the following factors: Due to the special properties required of rare earth oxides, dysprosium oxide (Dy2O3) is an important rare earth oxide with a unique 4f electronic structure, exhibiting excellent magnetic, optical, catalytic and nuclear properties.

[0003] Submicron materials exhibit size effects, with submicron (100-1000 nm) stability superior to nanoparticles. They are also easier to disperse and process, making them suitable for industrial applications (such as magnetic composites and ceramic sintering). Their optical and magnetic properties remain close to those of nanomaterials, but their preparation costs are lower.

[0004] The advantages of monodisperse spherical particles include: uniform physicochemical properties—consistent size avoids performance fluctuations (such as fluorescence quenching and uneven magnetic properties); excellent flowability—spherical particles are easier to disperse in powder processing (such as 3D printing and coating); and controllable surface chemistry—facilitating functional modification (such as biocompatible coatings and regulation of catalytic active sites).

[0005] However, Dy2O3 particles prepared by traditional methods are often uneven in size, irregular in morphology, and prone to agglomeration, which seriously affects their performance. Therefore, the development of monodisperse, spherical, and submicron-sized Dy2O3 has become a key research direction, and submicron-sized Dy2O3 has found a balance between performance and processability.

[0006] The current technological bottlenecks lie in: how to achieve monodisperse particle size preparation through precipitation; and how to solve the problem of sintering and agglomeration of particles in high-temperature applications. Overcoming these challenges will enable submicron-sized Dy2O3 to show promising application prospects. Summary of the Invention

[0007] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a monodisperse spherical dysprosium oxide particle with a particle size of less than 300 nm and its preparation method, which has good dispersibility and is not prone to agglomeration.

[0008] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: a method for preparing monodisperse spherical dysprosium oxide particles with a particle size of less than 300 nm, comprising the following steps: S1. Precipitate preparation process: a. Prepare a dysprosium chloride solution, then add a PEG-600 solution to it to obtain a dysprosium chloride-PEG mixture; prepare a urea solution; b. Add the dysprosium chloride-PEG mixture to the urea solution, ensuring complete hydrolysis, to obtain the initial material A mixture; c. Place the initial material A mixture in an electric furnace and heat it at a constant temperature. Adjust the pH to obtain precipitate A. d. Aging precipitate A, discarding the mother liquor, washing, and filtering to obtain precipitate B; S2. Calcination process: a. Place precipitate B into the crucible and open the lid; b. Place the crucible in a muffle furnace for calcination, and perform step-by-step temperature control calcination in three stages (air atmosphere, heating rate 5℃ / min).

[0009] S3. Ultrasonic process: Take out the dysprosium oxide and sonicate it with an ultrasonic power of 280-350W for 18-20 minutes.

[0010] Further, in the S1 precipitate preparation process a, dysprosium chloride is weighed and dissolved in pure water to prepare a 0.1 mol / L dysprosium chloride solution, and then a 10% PEG-600 solution is added to it. The two are mixed and stirred evenly to obtain a dysprosium chloride-PEG mixture, wherein the volume ratio of the dysprosium chloride solution to the PEG-600 solution is 1000 mL: 50 mL; urea is weighed and dissolved in pure water to prepare a 0.5 mol / L urea solution.

[0011] Furthermore, in the S1 precipitate preparation process b, the dysprosium chloride-PEG mixture from a is added to 2000 mL of urea solution to ensure complete hydrolysis and obtain the initial material A mixture.

[0012] Furthermore, in the S1 precipitate preparation process c, the initial material A mixture is heated in an electric furnace to 75-80℃ and kept at a constant temperature for 2-3 hours until the pH is 7, at which point precipitation is complete, and precipitate A is obtained.

[0013] Furthermore, in the S1 precipitate preparation process d, after aging precipitate A for 0.8-1 hour, the mother liquor is discarded, and the precipitate is washed 4-6 times with pure water and filtered to obtain precipitate B.

[0014] Furthermore, in the S2 calcination process b, the first stage is at a temperature of 200℃ for 1-2 hours.

[0015] Furthermore, in the S2 calcination process b, the second stage is at a temperature of 700℃ for 2-3 hours.

[0016] Furthermore, in the S2 calcination process b, the third stage is at a temperature of 790℃ for 2-3 hours.

[0017] Furthermore, it is prepared using the preparation method described in any one of claims 1 to 8.

[0018] (iii) Beneficial technical effects Monodispersity control: The uniform precipitation environment generated by the slow hydrolysis of urea is used to suppress local supersaturation, ensure synchronous nucleation, and form spherical particles, thereby reducing particle size distribution deviation from the source.

[0019] High-temperature sintering resistance design: Introducing a segmented calcination process, maintaining a constant heating rate for low-temperature demolding → medium-temperature crystallization → high-temperature short-term stabilization, and reducing particle surface energy by regulating the crystal phase transformation kinetics.

[0020] By combining ultrasonic cavitation to break down sintered oxides, the problem of particle migration and agglomeration at high temperatures can be solved.

[0021] The successful development of rare earth dysprosium oxide with submicron particles of <300nm is not only a breakthrough in size, but also signifies that the particles are highly uniform in size, morphology and composition due to their monodispersity, which has good application prospects in catalysis, biomedicine, magnetic materials and other fields. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with specific embodiments.

[0024] Example 1 A method for preparing monodisperse spherical dysprosium oxide particles with a particle size of less than 300 nm includes the following steps: S1. Precipitate preparation process: a. Weigh out dysprosium chloride and dissolve it in pure water to prepare a 0.1 mol / L dysprosium chloride solution. Then add a 10% (w / w) PEG-600 solution to the solution and mix them thoroughly to obtain a dysprosium chloride-PEG mixture. The volume ratio of the dysprosium chloride solution to the PEG-600 solution is 1000 mL: 50 mL. Weigh out urea and dissolve it in pure water to prepare a 0.5 mol / L urea solution. b. Add the dysprosium chloride-PEG mixture from a to 2000 mL of urea solution, ensuring complete hydrolysis to obtain the initial mixture A; c. Place the initial material A mixture in an electric furnace and heat it to 75°C. Maintain the temperature for 2 hours until the pH reaches 7, and the precipitation is complete, yielding precipitate A. d. After aging precipitate A for 0.8 hours, discard the mother liquor, wash with pure water 4 times, filter, and obtain precipitate B; S2. Calcination process: a. Place precipitate B into the crucible and open the lid; b. Place the crucible in a muffle furnace for calcination, and perform step-by-step temperature control calcination in three stages (air atmosphere, heating rate 5℃ / min); the first stage is at 200℃ for 1 hour; the second stage is at 700℃ for 2 hours; and the third stage is at 790℃ for 2 hours. S3. Ultrasonic process: Take out dysprosium oxide and sonicate it with an ultrasonic power of 280W for 18 minutes.

[0025] Example 2 A method for preparing monodisperse spherical dysprosium oxide particles with a particle size of less than 300 nm includes the following steps: S1. Precipitate preparation process: a. Weigh out dysprosium chloride and dissolve it in pure water to prepare a 0.1 mol / L dysprosium chloride solution. Then add a 10% (w / w) PEG-600 solution to the solution and mix them thoroughly to obtain a dysprosium chloride-PEG mixture. The volume ratio of the dysprosium chloride solution to the PEG-600 solution is 1000 mL: 50 mL. Weigh out urea and dissolve it in pure water to prepare a 0.5 mol / L urea solution. b. Add the dysprosium chloride-PEG mixture from a to 2000 mL of urea solution, ensuring complete hydrolysis to obtain the initial mixture A; c. Place the initial material A mixture in an electric furnace and heat it to 80°C. Maintain the temperature for 3 hours until the pH reaches 7, and the precipitation is complete, yielding precipitate A. d. After aging precipitate A for 1 hour, discard the mother liquor, wash with pure water 6 times, filter, and obtain precipitate B; S2. Calcination process: a. Place precipitate B into the crucible and open the lid; b. Place the crucible in a muffle furnace for calcination, and perform step-by-step temperature control calcination in three stages (air atmosphere, heating rate 5℃ / min); the first stage is at 200℃ for 2 hours; the second stage is at 700℃ for 3 hours; and the third stage is at 790℃ for 3 hours. S3. Ultrasonic process: Take out dysprosium oxide and sonicate it with an ultrasonic power of 350W for 20 minutes.

[0026] Example 3 A method for preparing monodisperse spherical dysprosium oxide particles with a particle size of less than 300 nm includes the following steps: S1. Precipitate preparation process: a. Weigh out dysprosium chloride and dissolve it in pure water to prepare a 0.1 mol / L dysprosium chloride solution. Then add a 10% (w / w) PEG-600 solution to the solution and mix them thoroughly to obtain a dysprosium chloride-PEG mixture. The volume ratio of the dysprosium chloride solution to the PEG-600 solution is 1000 mL: 50 mL. Weigh out urea and dissolve it in pure water to prepare a 0.5 mol / L urea solution. b. Add the dysprosium chloride-PEG mixture from a to 2000 mL of urea solution, ensuring complete hydrolysis to obtain the initial mixture A; c. Place the initial material A mixture in an electric furnace and heat it to 78°C. Maintain the temperature for 3 hours until the pH reaches 7, and the precipitation is complete, yielding precipitate A. d. After aging precipitate A for 0.9 hours, discard the mother liquor, wash with pure water 5 times, filter, and obtain precipitate B; S2. Calcination process: a. Place precipitate B into the crucible and open the lid; b. Place the crucible in a muffle furnace for calcination, and perform step-by-step temperature control calcination in three stages (air atmosphere, heating rate 5℃ / min); the first stage is at 200℃ for 1.5h; the second stage is at 700℃ for 2.5h; and the third stage is at 790℃ for 2.5h. S3. Ultrasonic process: Take out dysprosium oxide and sonicate it with an ultrasonic power of 320W for 19 minutes.

[0027] Example 4 A method for preparing monodisperse spherical dysprosium oxide particles with a particle size of less than 300 nm includes the following steps: S1. Precipitate preparation process: a. Weigh out dysprosium chloride and dissolve it in pure water to prepare a 0.1 mol / L dysprosium chloride solution. Then add a 10% (w / w) PEG-600 solution to the solution and mix them thoroughly to obtain a dysprosium chloride-PEG mixture. The volume ratio of the dysprosium chloride solution to the PEG-600 solution is 1000 mL: 50 mL. Weigh out urea and dissolve it in pure water to prepare a 0.5 mol / L urea solution. b. Add the dysprosium chloride-PEG mixture from a to 2000 mL of urea solution, ensuring complete hydrolysis to obtain the initial mixture A; c. Place the initial material A mixture in an electric furnace and heat it to 75°C. Maintain the temperature for 3 hours until the pH reaches 7, and the precipitation is complete, yielding precipitate A. d. After aging precipitate A for 0.8 hours, discard the mother liquor, wash with pure water 5 times, filter, and obtain precipitate B; S2. Calcination process: a. Place precipitate B into the crucible and open the lid; b. Place the crucible in a muffle furnace and calcine it in three stages with stepped temperature control (air atmosphere, heating rate 5℃ / min); the first stage is 200℃ for 2 hours; the second stage is 700℃ for 2 hours; and the third stage is 790℃ for 3 hours. S3. Ultrasonic process: Take out dysprosium oxide and sonicate it with an ultrasonic power of 350W for 18 minutes.

[0028] Table 1: Performance Tests

[0029] The experimental examples 1-4 above show that D50 < 300 nm and PDI < 0.25, which conforms to monodisperse spherical submicron particles. (Span is a relative width parameter calculated based on D10, D50, and D90, used to quantify the "width" of the particle size distribution. The smaller the value, the more concentrated the particle size distribution and the better the particle uniformity. Calculation formula: Span = (D90 - D10) / D50) It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0030] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0031] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments.

Claims

1. A method for producing monodisperse spherical particles of dysprosium oxide having a particle size of less than 300 nm, characterized in that, The method comprises the following steps: S1. Precipitate preparation process: a. Prepare a dysprosium chloride solution, and then add a PEG-600 solution to the dysprosium chloride solution to obtain a dysprosium chloride-PEG mixed solution; Prepare a urea solution; b. Add the dysprosium chloride-PEG mixed solution to the urea solution to ensure complete hydrolysis, to obtain a preliminary material A mixed solution; c. Heat the preliminary material A mixed solution in an electric furnace, keep the temperature constant, and adjust the pH to obtain precipitate A; d. Age the precipitate A, discard the mother liquor, wash, and suction filter to obtain precipitate B; S2. Calcination process: a. Put the precipitate B into a crucible and open the cover; b. Put the crucible into a muffle furnace for calcination, and perform stepwise temperature control calcination in three stages (air atmosphere, temperature rising rate of 5℃ / min); S3. Ultrasonic process: take out the dysprosium oxide and perform ultrasonic treatment, with an ultrasonic power of 280-350W and a time of 18-20min.

2. The method of producing monodispersed spherical particles of dysprosium oxide having a particle size of less than 300 nm according to claim 1, characterized in that, In the step a of the S1 precipitate preparation process, dysprosium chloride is weighed and dissolved in pure water to prepare a 0.1mol / L dysprosium chloride solution, and then a PEG-600 solution with a mass fraction of 10% is added to the dysprosium chloride solution, and the two are mixed and stirred uniformly to obtain a dysprosium chloride-PEG mixed solution, wherein the volume ratio of the dysprosium chloride solution to the PEG-600 solution is 1000mL:50mL; urea is weighed and dissolved in pure water to prepare a 0.5mol / L urea solution.

3. The method of producing monodispersed spherical particles of dysprosium oxide having a particle size of less than 300 nm according to claim 1, characterized in that, In the step b of the S1 precipitate preparation process, the dysprosium chloride-PEG mixed solution in step a is added to 2000mL of the urea solution to ensure complete hydrolysis, to obtain a preliminary material A mixed solution.

4. The method of producing monodispersed spherical particles of dysprosium oxide having a particle size of less than 300 nm according to claim 1, characterized in that, In the step c of the S1 precipitate preparation process, the preliminary material A mixed solution is heated to 75-80℃ in an electric furnace, and kept at the temperature for 2-3 hours until the pH is 7 and the precipitation is completed, to obtain precipitate A.

5. The method of producing monodispersed spherical particles of dysprosium oxide having a particle size of less than 300 nm according to claim 1, characterized in that, In the step d of the S1 precipitate preparation process, after the precipitate A is aged for 0.8-1 hour, the mother liquor is discarded, the precipitate A is washed with pure water for 4-6 times, and suction filtration is performed to obtain precipitate B.

6. The method of producing monodispersed spherical particles of dysprosium oxide having a particle size of less than 300 nm according to claim 1, characterized in that, In the step b of the S2 calcination process, the first stage is at a temperature of 200℃ for 1-2h.

7. The method of producing monodispersed spherical particles of dysprosium oxide having a particle size of less than 300 nm according to claim 1, characterized by, In the step b of the S2 calcination process, the second stage is at a temperature of 700℃ for 2-3h.

8. The method of producing monodispersed spherical particles of dysprosium oxide having a particle size of less than 300 nm according to claim 1, characterized by, In the step b of the S2 calcination process, the third stage is at a temperature of 790℃ for 2-3h.

9. Monodisperse spherical particles of dysprosium oxide having a particle size of less than 300 nm, characterized in that The method is prepared by the method of any one of claims 1-8.

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