Yttrium oxide powder and preparation method thereof

Abstract

The invention discloses yttrium oxide powder and a preparation method thereof. The preparation method of the yttrium oxide powder comprises the following steps: 1) mixing an yttrium salt solution with a precipitator solution to prepare a mixed solution; wherein the molar ratio of yttrium ions in the yttrium salt to the precipitant is 1: (2-15); 2) adding C2-C5 alkanediol into the mixed solution, and reacting at the temperature of 60-160 DEG C to prepare a precipitate precursor; and 3) calcining the precipitate precursor prepared in the step 2) at 500-1200 DEG C to prepare the yttrium oxide powder. The yttrium oxide powder prepared by the method is small in primary particle size and relatively narrow in particle size distribution.

Description

Technical Field

[0001] The invention relates to yttrium oxide powder and a preparation method thereof. Background Art

[0002] Yttrium oxide is an important rare earth oxide. As a representative of cubic sesquioxides, it has excellent physical, chemical and optical properties. When yttrium oxide is used as a matrix material, it has the advantages of high melting point (about 2430°C), high thermal conductivity (13.6W / m·k), good chemical stability, wide transmission band and low phonon energy. Yttrium oxide nanopowder has good optical, electrical, magnetic, mechanical and chemical properties, and is widely used in functional ceramic materials, medical imaging, luminescent materials, laser materials, exploration and many other fields. Nano yttrium oxide powder with smaller particle size is the key raw material for the preparation of transparent ceramics with excellent performance.

[0003] Existing methods for preparing nano yttrium oxide include combustion method, hydrothermal method, precipitation method, sol-gel method, etc. However, these methods all have certain defects. The main disadvantages are as follows: 1) When preparing yttrium oxide precursor, the preparation process takes too long, even up to 20 to 30 hours, and the production efficiency is low; 2) The primary particle size of the prepared yttrium oxide powder is too large, up to 20 to 60 μm, and does not belong to submicron or nanometer yttrium oxide ultrafine powder; 3) When preparing yttrium oxide precursor, the reaction temperature is too high, the energy consumption is high, and the requirements for corresponding equipment are high. In addition, in the prior art, the ion concentration in the reaction system of the precipitant and the yttrium salt is uneven, which makes it difficult to control the nucleation and growth rate of the precipitation, resulting in a large particle size of the yttrium oxide powder and a wide particle size distribution. Therefore, how to produce nano yttrium oxide powder with a smaller particle size using a simple preparation process has become a technical problem that needs to be solved in this field.

[0004] CN101698609A discloses a method for preparing spherical, monodisperse, single-size yttrium oxide nanopowders. The method adds urea to an aqueous solution containing yttrium ions and adopts a homogeneous precipitation method to prepare spherical, monodisperse rare earth ion-doped yttrium oxide nanopowders. As can be seen from the embodiments, the nano-scale yttrium oxide powder prepared by the method is yttrium oxide powder doped with other rare earth elements, and the method needs to be freeze-dried at 20Pa and -50°C, and the preparation requirements are relatively high.

[0005] CN110330048A discloses a method for preparing nano yttrium oxide powder. The method first prepares an aqueous solution of yttrium salt and an aqueous solution of a precipitant mixed with a surfactant; the two are mixed to cause a precipitation reaction, and after obtaining a precipitate, the precipitate is calcined in stages to obtain nano yttrium oxide powder. The method requires adding a surfactant to the precipitant solution, the aqueous solution of yttrium salt and the aqueous solution of the precipitant mixed with a surfactant need to be added dropwise and mixed, and the generated precipitate needs to be calcined in three stages, and the preparation process is complicated.

[0006] CN106044835A discloses a method for preparing nano-scale spherical yttrium oxide powder. The method comprises the following steps: -1 Add yttrium salt solution with a concentration of 0.5-1 mol·L -1 The precipitant solution is stirred and dissolved to obtain a mixed solution, and a surfactant is added at 0.2-2% of the mass of the mixed solution to obtain an yttrium oxide precursor precipitate. After solid-liquid separation, the precipitate is washed with water and a small molecule alcohol respectively, and the precipitate suspension is treated with ultrasonic dispersion. After separation, drying, and calcination, an yttrium oxide powder composed of nano-scale spherical particles is obtained; the surfactant is composed of a cationic surfactant and a non-ionic surfactant. The method requires the addition of a cationic surfactant and a non-ionic surfactant to the mixed solution, and the preparation process also requires ultrasonic dispersion.

[0007] CN118206148A discloses a method for preparing yttrium oxide particle clusters. The method comprises: dissolving yttrium salt in a mixed solution of deionized water and surfactant to form solution A; dissolving a mineralizer in deionized water to form solution B; mixing the solution B with the solution A, and adjusting the pH with an alkali solution until a white colloidal suspension is formed; subjecting the white colloidal suspension to a hydrothermal reaction to obtain a yttrium oxide precursor; and treating the yttrium oxide precursor to obtain yttrium oxide particle clusters. The method requires adding a surfactant to the yttrium salt aqueous solution, and what is prepared is yttrium oxide particle clusters with a size of 6.60 to 14.88 μm rather than nano-scale yttrium oxide powder. Summary of the invention

[0008] In view of this, one object of the present invention is to provide a method for preparing yttrium oxide powder. In the preparation method, alkanediol is added when preparing a precursor, and the primary particle size of the obtained yttrium oxide powder is small and the particle size distribution is narrow. Another object of the present invention is to provide yttrium oxide powder obtained by the above preparation method.

[0009] The present invention adopts the following technical solutions to achieve the above-mentioned purpose.

[0010] In one aspect, the present invention provides a method for preparing yttrium oxide powder, comprising the following steps:

[0011] 1) mixing a yttrium salt solution with a precipitant solution to obtain a mixed solution; wherein the molar ratio of yttrium ions in the yttrium salt to the precipitant is 1:(2-15); the precipitant is at least one selected from urea, carbonate, bicarbonate, and hydroxide;

[0012] 2) adding C2-C5 alkanediol to the mixed solution and reacting at 60-160° C. to obtain a precipitate precursor;

[0013] 3) calcining the precipitate precursor obtained in step 2) at 500-1200° C. to obtain yttrium oxide powder.

[0014] According to the preparation method of the present invention, preferably, in step 1), the concentration of the yttrium salt solution is 0.05-5 mol / L, and the concentration of the precipitant solution is 0.05-5 mol / L.

[0015] According to the preparation method of the present invention, preferably, in step 1), the yttrium salt is selected from at least one of yttrium nitrate, yttrium halide, yttrium acetate and yttrium sulfate.

[0016] According to the preparation method of the present invention, preferably, in step 1), the carbonate is selected from at least one of alkali metal carbonates and (NH4)2CO3; the bicarbonate is selected from at least one of alkali metal bicarbonate and NH4HCO3; the hydroxide is selected from at least one of alkali metal hydroxide and ammonia monohydrate.

[0017] According to the preparation method of the present invention, preferably, in step 2), the volume ratio of C2-C5 alkanediol to the mixed liquid is 1:(0.5-5);

[0018] The C2-C5 alkanediol is a C2-C4 alkanediol.

[0019] According to the preparation method of the present invention, preferably, in step 2), the reaction time is 1 to 10 hours.

[0020] According to the preparation method of the present invention, preferably, step 2) further comprises the steps of filtering, washing and drying the obtained precipitate precursor.

[0021] According to the preparation method of the present invention, preferably, the washing uses at least one of water and C1-C5 alkyl alcohol; the drying temperature is 40-100° C., and the drying time is 10-48 hours.

[0022] According to the preparation method of the present invention, preferably, in step 3), the calcination time is 1 to 8 hours.

[0023] On the other hand, the present invention also provides an yttrium oxide powder prepared by any of the above-mentioned preparation methods, wherein the primary particle size D of the yttrium oxide powder is 50 It is 10 to 50 nm.

[0024] In the present invention, alkanediol is added during the preparation of the precursor, and the obtained yttrium oxide powder has a small primary particle size, a narrow particle size distribution, and a uniform morphology. At the same time, the present invention also has the advantages of short preparation time, mild reaction conditions, and simple operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is an electron microscope image of the yttrium oxide powder prepared in Example 1 of the present invention.

[0026] Figure 2 This is an electron microscope image of yttrium oxide powder prepared in Comparative Example 1 of the present invention.

[0027] Figure 3 This is an electron microscope image of yttrium oxide powder prepared in Comparative Example 2 of the present invention.

[0028] Figure 4 The particle size distribution of the yttrium oxide powder prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0030] The "primary particle size" mentioned in the present invention, also called the original particle size or the initial particle size, refers to the particle size of a single fine grain in the powder, and the unit is nanometer (nm).

[0031] <Method for preparing yttrium oxide powder>

[0032] The method for preparing yttrium oxide powder of the present invention comprises a raw material mixing step, a precursor preparation step and a calcination step, and further comprises the steps of filtering, washing and drying the precursor, which is described in detail below.

[0033] Raw material mixing steps

[0034] The yttrium salt solution and the precipitant solution are mixed to obtain a mixed solution.

[0035] According to one embodiment of the present invention, the yttrium salt can be selected from at least one of yttrium nitrate, yttrium halide, yttrium acetate, and yttrium sulfate; preferably at least one of yttrium nitrate, yttrium halide, and yttrium acetate; more preferably at least one of yttrium nitrate, yttrium chloride, yttrium bromide, and yttrium acetate.

[0036] According to one embodiment of the present invention, the precipitant can be selected from at least one of urea, carbonates, bicarbonates, and hydroxides; preferably at least one of urea, alkali metal carbonates, (NH4)2CO3, alkali metal bicarbonates, NH4HCO3, and alkali metal hydroxides; more preferably at least one of urea, alkali metal carbonates, (NH4)2CO3; most preferably urea.

[0037] According to one embodiment of the present invention, the alkali metal carbonate may be selected from at least one of Li2CO3, Na2CO3, and K2CO3; preferably at least one of Na2CO3 and K2CO3; more preferably Na2CO3 or K2CO3.

[0038] The alkali metal bicarbonate can be selected from at least one of LiHCO3, NaHCO3, and KHCO3; preferably at least one of NaHCO3 and KHCO3; more preferably NaHCO3 or KHCO3.

[0039] The hydroxide may be selected from at least one of an alkali metal hydroxide and ammonia monohydrate, preferably at least one of LiOH, NaOH and KOH, and more preferably at least one of NaOH and KOH.

[0040] According to one embodiment of the present invention, the molar ratio of yttrium ions in the yttrium salt to the precipitant may be 1:(2-15); preferably 1:(2-12); more preferably 1:(4-10).

[0041] According to one embodiment of the present invention, the concentration of the yttrium salt solution may be 0.05 to 5 mol / L; preferably 0.05 to 3 mol / L; more preferably 0.1 to 3 mol / L.

[0042] The concentration of the precipitant solution may be 0.05 to 5 mol / L, preferably 0.1 to 3 mol / L, and more preferably 0.4 to 3 mol / L.

[0043] Reasonable concentration and dosage of yttrium salt and precipitant are conducive to the formation of a stable precipitate precursor, and are more conducive to the generation of yttrium oxide powder with uniform morphology, small primary particle size and narrow particle size distribution.

[0044] The raw materials used in the present invention can be commercially available products or prepared by existing preparation methods, and are not particularly limited here. The purity of the raw materials of the present invention is at least industrial purity (99.9wt%).

[0045] The water used in the present invention can be deionized water or ultrapure water; preferably deionized water.

[0046] Precursor preparation steps

[0047] Add C2-C5 alkanediol to the mixed solution, react at 60-160° C. to obtain a precipitate precursor. In the present invention, alkanediol is added when preparing the precursor, and the obtained yttrium oxide powder has a small primary particle size, a narrow particle size distribution, and a uniform morphology.

[0048] According to one embodiment of the present invention, the volume ratio of C2-C5 alkane diol to the mixed liquid may be 1:(0.5-5); preferably 1:(1-5); more preferably 1:(1-3).

[0049] According to one embodiment of the present invention, the C2-C5 alkane diol may be a C2-C4 alkane diol; preferably at least one of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butanediol; more preferably at least one of ethylene glycol, 1,2-propylene glycol, and 1,4-butanediol.

[0050] C2-C5 alkanediol is a polar solvent that can dissolve inorganic metal salts to form a solution. It has a high boiling point and can provide a higher reaction temperature. It has a strong reducing property at high temperature.

[0051] The present invention mainly contains two types of components in the initial reaction system: metal oxide precursor and organic solvent. The organic solvent acts as a reducing agent in the reaction process, which connects to the particle surface and limits the crystal growth rate and affects the morphology and assembly of the particles. The present invention uses C2-C5 alkanediol as an organic solvent, which has high viscosity characteristics and large viscous resistance, can reduce the Brownian motion of solute molecules, greatly reduce the high surface tension of the particle powder surface, and thus is conducive to the preparation of nanopowders with controllable particle size and narrow distribution.

[0052] According to one embodiment of the present invention, the reaction temperature may be 60 to 160°C; preferably 65 to 150°C; more preferably 80 to 120°C.

[0053] According to another embodiment of the present invention, the reaction time may be 1 to 10 hours; preferably 2 to 9 hours; more preferably 2 to 8 hours.

[0054] According to one embodiment of the present invention, the heating rate of the reaction may be 1 to 10°C / min, preferably 2 to 8°C / min, and more preferably 3 to 5°C / min.

[0055] According to one embodiment of the present invention, stirring may be performed during the reaction.

[0056] According to a specific embodiment of the present invention, the reaction can be carried out in an oil bath magnetic stirrer.

[0057] Limiting the reaction conditions within the above range is conducive to forming a stable precipitate precursor, and is more conducive to generating yttrium oxide powder with uniform morphology, small primary particle size and narrow particle size distribution.

[0058] The present invention may further include the steps of filtering, washing and drying the obtained precipitate precursor.

[0059] In the present invention, filtration can be performed by any filtration method known in the art, without particular limitation, such as gravity filtration, pressure filtration, centrifugal filtration, vacuum filtration, etc. Various filtration methods can be performed using equipment known in the art.

[0060] According to one embodiment of the present invention, the detergent can use at least one of water and C1-C5 alkyl alcohols; preferably, water and at least one of C1-C3 alkyl alcohols are used; more preferably, water and at least one of C1-C3 normal alkyl alcohols are used; most preferably, at least one of deionized water, methanol, ethanol, and normal propanol is used.

[0061] In the present invention, the C1-C5 alkyl alcohol may include but is not limited to methanol, ethanol, propanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, neopentyl alcohol and the like.

[0062] The washing times in the present invention can be 1 to 6 times, preferably 2 to 5 times, and more preferably 3 to 5 times. The washing method can be washing with one detergent or washing with different detergents at different washing times, which is not particularly limited here.

[0063] According to one embodiment of the present invention, the drying temperature may be 40 to 100°C; preferably 45 to 95°C; more preferably 50 to 80°C.

[0064] According to another embodiment of the present invention, the drying time may be 10 to 48 hours, preferably 12 to 42 hours, and more preferably 15 to 36 hours.

[0065] Calcination step

[0066] The precipitate precursor is calcined at 500-1200° C. to obtain yttrium oxide powder.

[0067] According to one embodiment of the present invention, the calcination temperature may be 500-1200°C; preferably 600-1000°C; more preferably 650-950°C.

[0068] According to another embodiment of the present invention, the calcination time may be 1 to 8 hours, preferably 2 to 6 hours, and more preferably 2 to 4 hours.

[0069] According to one embodiment of the present invention, the heating rate of calcination may be 5 to 30° C. / min, preferably 8 to 25° C. / min, and more preferably 10 to 20° C. / min.

[0070] In the present invention, calcination can be carried out in any high temperature resistant equipment known in the art, and is not particularly limited herein, for example, in a high temperature sintering furnace or a muffle furnace.

[0071] The present invention can also cool the obtained yttrium oxide powder after calcination.

[0072] In the present invention, cooling can be achieved by any cooling method known in the art, and is not particularly limited here. For example, it can be natural cooling or air cooling.

[0073] <Yttrium oxide powder>

[0074] The yttrium oxide powder of the present invention can be prepared by adopting the above-mentioned method for preparing yttrium oxide powder.

[0075] According to one embodiment of the present invention, the primary particle size of the prepared yttrium oxide powder may be 10 to 50 nm, preferably 20 to 40 nm, and more preferably 20 to 30 nm.

[0076] <Test Method>

[0077] The primary particle size of yttrium oxide powder was measured using a Sigma 500 electron microscope produced by ZEISS.

[0078] Determination of particle size distribution of yttrium oxide powder: NanoBrook90Plus PALS nanoparticle size analyzer produced by Brookhaven Instruments, USA was used for testing.

[0079] <Ingredients>

[0080] The other raw materials in the following examples are all commercially available products unless otherwise specified.

[0081] Example 1

[0082] Weigh yttrium nitrate and urea respectively and dissolve them in deionized water to prepare a 0.1 mol / L yttrium nitrate solution and a 0.6 mol / L urea solution. Mix 50 mL of the yttrium nitrate solution and 50 mL of the urea solution to prepare a mixed solution.

[0083] 80 mL of ethylene glycol was added to the mixed solution, and the temperature was raised to 90°C at a heating rate of 5°C / min under stirring, and the mixture was stirred at 90°C for 2 h to obtain a precipitate. The precipitate was centrifuged and washed with deionized water for 3 times, and then dried at 60°C for 24 h to obtain a precipitate precursor.

[0084] The precipitate precursor was placed in a muffle furnace, heated to 900°C at a heating rate of 15°C / min, and calcined at 900°C for 4 hours. After calcination, it was cooled to room temperature in air to obtain yttrium oxide powder.

[0085] Example 2

[0086] Weigh yttrium nitrate and urea respectively and dissolve them in deionized water to prepare a 0.1 mol / L yttrium nitrate solution and a 0.6 mol / L urea solution. Mix 50 mL of yttrium nitrate solution and 80 mL of urea solution to prepare a mixed solution.

[0087] 40 mL of ethylene glycol was added to the mixed solution, and the temperature was raised to 120°C at a heating rate of 5°C / min under stirring, and the reaction was stirred at 120°C for 6 hours to obtain a precipitate. The precipitate was centrifuged and washed 3 times with deionized water, then washed 2 times with ethanol, and then dried at 60°C for 24 hours to obtain a precipitate precursor.

[0088] The precipitate precursor was placed in a muffle furnace, heated to 650°C at a heating rate of 15°C / min, and calcined at 650°C for 4 hours. After calcination, it was cooled to room temperature in air to obtain yttrium oxide powder.

[0089] Comparative Example 1

[0090] The only difference from Example 1 is that no ethylene glycol is added.

[0091] Comparative Example 2

[0092] The only difference from Example 1 is that polyethylene glycol is used instead of ethylene glycol.

[0093] Experimental Example 1

[0094] The yttrium oxide powders obtained in Example 1, Comparative Example 1 and Comparative Example 2 were observed under an electron microscope. Figures 1 to 3 As shown. Figures 1 to 3 It can be seen that the particles of the yttrium oxide powder prepared in Example 1 are spherical and have a uniform morphology. The primary particle size D of the yttrium oxide powder 50 The particle morphology of the yttrium oxide powders prepared in Comparative Examples 1 and 2 is irregular and agglomerated.

[0095] The particle size distribution of the yttrium oxide powder prepared in Example 1 is as follows: Figure 4 As shown. Figure 4 It can be seen that the particle size distribution of the yttrium oxide powder prepared in Example 1 is relatively narrow.

[0096] The present invention is not limited to the above-mentioned embodiments. Without departing from the essential content of the present invention, any deformation, improvement and substitution that can be conceived by those skilled in the art shall fall within the scope of the present invention.

Claims

1. A method for preparing yttrium oxide powder, comprising the following steps: 1) mixing a yttrium salt solution with a precipitant solution to obtain a mixed solution; wherein the molar ratio of yttrium ions in the yttrium salt to the precipitant is 1:(2-15); the precipitant is at least one selected from urea, carbonate, bicarbonate, and hydroxide; 2) adding C2-C5 alkanediol to the mixed solution and reacting at 60-160° C. to obtain a precipitate precursor; 3) calcining the precipitate precursor obtained in step 2) at 500-1200° C. to obtain yttrium oxide powder.

2. The preparation method according to claim 1, characterized in that: In step 1), the concentration of the yttrium salt solution is 0.05-5 mol / L, and the concentration of the precipitant solution is 0.05-5 mol / L.

3. The preparation method according to claim 1, characterized in that: In step 1), the yttrium salt is selected from at least one of yttrium nitrate, yttrium halide, yttrium acetate and yttrium sulfate.

4. The preparation method according to claim 1, characterized in that: In step 1), the carbonate is selected from at least one of alkali metal carbonates and (NH4)2CO3; the bicarbonate is selected from at least one of alkali metal bicarbonate and NH4HCO3; and the hydroxide is selected from at least one of alkali metal hydroxide and ammonia monohydrate.

5. The preparation method according to claim 1, characterized in that: In step 2), the volume ratio of C2-C5 alkanediol to the mixed solution is 1:(0.5-5); The C2-C5 alkanediol is a C2-C4 alkanediol.

6. The preparation method according to claim 1, characterized in that: In step 2), the reaction time is 1 to 10 hours.

7. The preparation method according to claim 1, characterized in that: Step 2) also includes the steps of filtering, washing and drying the obtained precipitate precursor.

8. The preparation method according to claim 7, characterized in that: The washing uses at least one of water and C1-C5 alkyl alcohol; The drying temperature is 40-100° C., and the drying time is 10-48 hours.

9. The preparation method according to claim 1, characterized in that: In step 3), the calcination time is 1 to 8 hours.

10. A yttrium oxide powder obtained by the preparation method according to any one of claims 1 to 9, characterized in that: The primary particle size D of the yttrium oxide powder 50 It is 10 to 50 nm.

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