Method of preparing cerium boride powder

Abstract

A method of preparing cerium boride powder, according to the present invention, includes a first step for generating mixed powder by mixing at least one selected from among cerium chloride (CeCl.sub.3) powder and cerium oxide (CeO.sub.2) powder, at least one selected from among magnesium hydride (MgH.sub.2) powder and magnesium (Mg) powder, and boron oxide (B.sub.2O.sub.3) powder, a second step for generating composite powder including cerium boride (Ce.sub.xB.sub.y) and at least one selected from among magnesium oxide (MgO) and magnesium chloride (MgCl.sub.2), by causing reaction in the mixed powder at room temperature based on a ball milling process, and a third step for selectively depositing cerium boride powder by dispersing the composite powder in a solution.

Claims

1. A method of preparing cerium boride powder, the method comprising: a first step, for generating a mixed powder, by mixing magnesium hydride (MgH.sub.2) powder, boron oxide (B.sub.2O.sub.3) powder, and at least one selected from the group consisting of cerium (III) chloride (CeCl.sub.3) powder and cerium (IV) oxide (CeO.sub.2) powder; a second step, for generating a composite powder comprising cerium boride (CeB.sub.6) and at least one selected from the group consisting of magnesium oxide (MgO) and magnesium chloride (MgCl.sub.2), of reacting the mixed powder at room temperature in a ball milling process; and a third step, for selectively depositing cerium boride powder, of dispersing the composite powder in a solution.

2. The method of claim 1, wherein the first step comprises generating the mixed powder by mixing the CeCl.sub.3 powder, the MgH.sub.2 powder, and the B.sub.2O.sub.3 powder, and wherein the third step comprises selectively dissolving MgCl.sub.2 and MgO and selectively depositing the cerium boride powder by dispersing the composite powder in an acidic solution.

3. The method of claim 1, wherein the first step comprises generating the mixed powder by mixing the CeCl.sub.3 powder, the MgH.sub.2 powder, and the B.sub.2O.sub.3 powder, and wherein the third step comprises selectively dissolving MgCl.sub.2 and obtaining deposited powder by dispersing the composite powder in a solution and removing MgO and obtaining the cerium boride powder by adding acid to the deposited powder.

4. The method of claim 1, wherein the first step comprises generating the mixed powder by mixing the CeO.sub.2 powder, the MgH.sub.2 powder, and the B.sub.2O.sub.3 powder, and wherein the third step comprises selectively dissolving MgO and selectively depositing the cerium boride powder by dispersing the composite powder in an acidic solution.

5. The method of claim 1, wherein, in the second step, the ball milling process comprises a process of putting balls and the mixed powder in a reaction vessel, filling air, argon (Ar), helium (He), nitrogen (N.sub.2), or hydrogen (H.sub.2) gas in the reaction vessel, and then performing ball milling.

6. The method of claim 5, wherein the ball milling process comprises a high-energy ball milling process selected from a process consisting of a shaker mill process, a vibratory mill process, a planetary mill process, and an attritor mill process.

7. The method of claim 1, wherein, in the third step, the cerium boride powder has a particle size equal to or less than 5 m and a crystal grain size of 20 nm.

8. The method of claim 1, wherein the third step is performed at room temperature.

9. The method of claim 1, wherein the cerium boride powder prepared using the mixed powder comprising the MgH.sub.2 powder has a crystal grain size less than a crystal grain size of a cerium boride powder prepared using a mixed powder comprising Mg powder.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and other features and advantages of the present invention will become more apparent by describing in detail embodiments thereof with reference to the attached drawings in which:

(2) FIG. 1 is a flowchart of a method of preparing cerium boride powder, according to an embodiment of the present invention;

(3) FIG. 2 is a graph showing X-ray diffraction patterns of composite powder (1) obtained by performing high-energy ball milling on mixed powder of boron oxide (B.sub.2O.sub.3) powder, cerium chloride (CeCl.sub.3) powder, and magnesium hydride (MgH.sub.2) powder, and cerium boride powder (2) obtained by selectively removing magnesium oxide (MgO) and magnesium chloride (MgCl.sub.2) from the composite powder (1) by using an acidic solution;

(4) FIG. 3 is a scanning electron microscopy (SEM) image of cerium boride powder prepared according to the present invention;

(5) FIG. 4 is a graph showing a result of analyzing the cerium boride powder prepared according to the present invention, by using a laser particle size analyzer;

(6) FIG. 5 is a graph showing X-ray diffraction patterns of composite powder (1) obtained by performing high-energy ball milling on mixed powder of B.sub.2O.sub.3 powder, cerium oxide (CeO.sub.2) powder, and MgH.sub.2 powder, and cerium boride powder (2) obtained by selectively removing MgO from the composite powder (1) by using an acidic solution;

(7) FIG. 6 is a graph showing X-ray diffraction patterns of composite powder (1) obtained by performing high-energy ball milling on mixed powder of B.sub.2O.sub.3 powder, CeCl.sub.3 powder, and magnesium (Mg) powder, and cerium boride powder (2) obtained by selectively removing MgO and MgCl.sub.2 from the composite powder (1) by using an acidic solution;

(8) FIG. 7A shows a dark field image obtained by performing transmission electron microscopy (TEM) analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and MgH.sub.2 powder;

(9) FIG. 7B shows a bright field image obtained by performing transmission electron microscopy (TEM) analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and MgH.sub.2 powder;

(10) FIG. 7C shows a composition mapping image obtained by performing transmission electron microscopy (TEM) analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and MgH.sub.2 powder;

(11) FIG. 7D shows an electron diffraction pattern image obtained by performing transmission electron microscopy (TEM) analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and MgH.sub.2 powder;

(12) FIG. 8A shows a dark field image obtained by performing TEM analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and Mg powder;

(13) FIG. 8B shows a bright field image obtained by performing TEM analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and Mg powder;

(14) FIG. 8C shows a composition mapping image obtained by performing TEM analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and Mg powder; and

(15) FIG. 8D shows an electron diffraction pattern image obtained by performing TEM analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and Mg powder.

DETAILED DESCRIPTION

(16) The present invention will now be described more fully with reference to the accompanying drawings, in which embodiments of the invention are shown. The invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein, rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to one of ordinary skill in the art. In the drawings, like reference numerals denote like elements and the sizes of at least some elements may be exaggerated or reduced for clarity of explanation.

(17) The terminology used herein is for the purpose of describing particular embodiments and is not intended to limit the invention. As used herein, the singular forms a, an, and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

(18) Unless defined differently, all terms used in the description including technical and scientific terms have the same meaning as generally understood by one of ordinary skill in the art. Terms as defined in a commonly used dictionary should be construed as having the same meaning as in an associated technical context, and unless defined in the description, the terms are not ideally or excessively construed as having formal meaning. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention unclear.

(19) The present invention provides a method of economically preparing cerium boride powder having a particle size equal to or less than 5 m and a small crystal grain size of about 20 nm by performing high-energy ball milling on mixed powder of boron oxide (B.sub.2O.sub.3) powder, one or a combination of magnesium (Mg) powder and magnesium hydride (MgH.sub.2) powder, and one or a combination of cerium chloride (CeCl.sub.3) powder and cerium oxide (CeO.sub.2) powder at room temperature in a vessel filled with air, inert gas, or hydrogen (H.sub.2) gas.

(20) The present invention relates to a method of preparing cerium boride powder and, more particularly, to a method of preparing cerium boride powder by mixing B.sub.2O.sub.3 powder, one or a combination of Mg powder and MgH.sub.2 powder, and one or a combination of CeCl.sub.3 powder and CeO.sub.2 powder and causing chemical reaction between particles of the mixed powder based on high-energy ball milling.

(21) That is, the present invention relates to a method of preparing cerium boride (Ce.sub.xB.sub.y) powder by causing mechanical chemical reaction in mixed power of B.sub.2O.sub.3 powder, one or a combination of Mg powder and MgH.sub.2 powder, and one or a combination of CeCl.sub.3 powder and CeO.sub.2 powder based on high-energy ball milling, removing by-products of reaction, e.g., MgO and MgCl.sub.2, from the powder, and collecting CeB.sub.6 powder. According to the present invention, cerium boride powder having a crystal grain size of about 20 nm and a particle size equal to or less than 5 m may be economically prepared at room temperature based on a simple process.

(22) A method of preparing cerium boride powder, according to the present invention, includes mixing B.sub.2O.sub.3 powder, one or a combination of Mg powder and MgH.sub.2 powder, and one or a combination of CeCl.sub.3 powder and CeO.sub.2 powder, putting the mixture in a reaction vessel together with balls and filling air, argon (Ar), helium (He), nitrogen (N.sub.2), or hydrogen (H.sub.2) gas in the reaction vessel, synthesizing Ce.sub.xB.sub.y, MgO and MgCl.sub.2 by performing high-energy ball milling on the mixture, selectively removing MgO and MgCl.sub.2 from the reaction product by using an acidic solution, and depositing and collecting cerium boride powder.

(23) Provided is a method of preparing cerium boride powder, the method including mixing B.sub.2O.sub.3 powder, one or a combination of MgH.sub.2 powder and Mg powder, and one or a combination of CeCl.sub.3 powder and CeO.sub.2 powder at a mole ratio of a:b:c:d:e, generating composite powder including Ce.sub.xB.sub.y, MgO, and MgCl.sub.2 by putting the mixed powder in a reaction vessel together with balls, filling air, Ar, He, N.sub.2, or H.sub.2 gas in the reaction vessel, and then performing high-energy ball milling, selectively dissolving MgCl.sub.2 and MgO and selectively depositing and separating cerium boride powder by dispersing the generated composite powder in an acidic solution. Herein, a, b, c, d, e, x, and y are real numbers.

(24) Embodiments of the present invention will now be described in detail with reference to the attached drawings.

(25) FIG. 1 is a flowchart of a method of preparing cerium boride powder, according to an embodiment of the present invention.

(26) Referring to FIG. 1, the method of preparing cerium boride powder, according to an embodiment of the present invention, includes a first step S100 for generating mixed powder by mixing at least one selected from among cerium chloride (CeCl.sub.3) powder and cerium oxide (CeO.sub.2) powder, at least one selected from among magnesium hydride (MgH.sub.2) powder and magnesium (Mg) powder, and boron oxide (B.sub.2O.sub.3) powder, a second step S200 for generating composite powder including cerium boride (Ce.sub.xB.sub.y) and at least one selected from among magnesium oxide (MgO) and magnesium chloride (MgCl.sub.2), by causing reaction in the mixed powder at room temperature based on a ball milling process, and a third step S300 for selectively depositing cerium boride powder by dispersing the composite powder in a solution.

(27) According to an example of the method of preparing cerium boride powder, the first step S100 may include generating the mixed powder by mixing the CeCl.sub.3 powder, the MgH.sub.2 powder, and the B.sub.2O.sub.3 powder, and the third step S300 may include selectively dissolving MgCl.sub.2 and MgO and selectively depositing the cerium boride powder by dispersing the composite powder in an acidic solution. According to a modified example thereof, the third step S300 may include selectively dissolving MgCl.sub.2 and obtaining deposited powder by dispersing the composite powder in a solution, and removing MgO and obtaining the cerium boride powder by adding acid to the deposited powder that is not necessarily acidic.

(28) According to another example of the method of preparing cerium boride powder, the first step S100 may include generating the mixed powder by mixing the CeO.sub.2 powder, the MgH.sub.2 powder, and the B.sub.2O.sub.3 powder, and the third step S300 may include selectively dissolving MgO and selectively depositing the cerium boride powder by dispersing the composite powder in an acidic solution. According to a modified example thereof, the third step S300 may include obtaining deposited powder by dispersing the composite powder in a solution that is not necessarily acidic, and removing MgO and obtaining the cerium boride powder by adding acid to the deposited powder.

(29) According to another example of the method of preparing cerium boride powder, the first step S100 may include generating the mixed powder by mixing the CeO.sub.2 powder, the Mg powder, and the B.sub.2O.sub.3 powder, and the third step S300 may include selectively dissolving MgO and selectively depositing the cerium boride powder by dispersing the composite powder in an acidic solution. According to a modified example thereof, the third step S300 may include obtaining deposited powder by dispersing the composite powder in a solution that is not necessarily acidic, and removing MgO and obtaining the cerium boride powder by adding acid to the deposited powder.

(30) Based on the method of preparing cerium boride powder, according to the present invention, in the first step S100, the mixed powder is generated by mixing the CeCl.sub.3 powder, the CeO.sub.2 powder, the B.sub.2O.sub.3 powder, the Mg powder, and the MgH.sub.2 powder at a mole ratio of a:b:c:d:e, where a, b, c, d, and e are zero or positive real numbers.

(31) In the second step S200, the mixed powder is put in a vessel together with balls, air, inert gas, or hydrogen (H.sub.2) gas is filled in the vessel, and then high-energy ball milling is performed using a shaker mill, a vibratory mill, a planetary mill, or an attritor mill. As such, Ce.sub.xB.sub.y, MgCl.sub.2, and MgO are synthesized by causing reaction between particles of the mixed powder as shown below. H.sub.2 gas generated due to the reaction is discharged when the vessel is open.
aCeCl.sub.3+bCeO.sub.2+cB.sub.2O.sub.3+dMg+eMgH.sub.2.fwdarw.Ce.sub.xB.sub.y+fMgO+gMgCl.sub.2+hH.sub.2,

(32) where a, b, c, d, e, f, g, h, x, and y are zero or positive real numbers.

(33) The composite powder generated in the second step S200 may include at least one selected from among MgO and MgCl.sub.2. When the mixed power of the first step S100 includes the CeCl.sub.3 powder, the composite powder may include MgCl.sub.2.

(34) In the third step S300 for selectively depositing the cerium boride powder by dispersing the composite powder in the solution, the solution may be an acidic solution. MgO and MgCl.sub.2 may be dissolved in the acidic solution. MgCl.sub.2 may also be dissolved a non-acidic solution but MgO may not be easily dissolved a non-acidic solution.

(35) After the composite powder is dispersed in the acidic solution, the cerium boride powder is deposited and collected at room temperature in an air atmosphere. In this process, MgCl.sub.2 may be dissolved in the solution and MgO may be removed from Ce.sub.xB.sub.y by acid.

Embodiment 1

(36) According to the process order of FIG. 1, CeCl.sub.3 powder, B.sub.2O.sub.3 powder, and MgH.sub.2 powder are mixed at a mole ratio of 2:6:21, the mixed powder is put in a high-speed steel vessel in an air atmosphere together with six 12.7-mm-diameter chromium (Cr) steel balls and two 10-mm-diameter Cr steel balls at a weight ratio of about 1:39, and then high-energy ball milling is performed using a shaker mill for 2 hours. The milled powder is dispersed in acid-added ethanol and then deposited powder is collected.

(37) FIG. 2 is a graph showing X-ray diffraction patterns of the milled powder (1) and the powder (2) collected from the acidic solution. The X-ray diffraction pattern of the milled powder (1) shows that CeB.sub.6 and MgO are well synthesized due to chemical reaction using high-energy ball milling. MgCl.sub.2 is amorphized due to room temperature milling and is not shown on the X-ray diffraction pattern. The X-ray diffraction pattern of the powder (2) collected from the acidic solution shows that only pure CeB.sub.6 is well collected. It is also shown that, since particles of the cerium boride powder have a very small crystal grain size, peaks of the X-ray diffraction pattern are broadened. The crystal grain size calculated using the Scherrer equation based on full width at half maximum (FWHM) values of the peaks is about 20 nm.

(38) FIG. 3 is a scanning electron microscopy (SEM) image of the cerium boride powder prepared using the method of Embodiment 1. It is shown that most particles of the powder have an irregular shape and have a small particle size equal to or less than 5 m.

(39) FIG. 4 is a graph showing a result of analyzing a particle size of the cerium boride powder prepared using the method of Embodiment 1, by using a laser particle size analyzer. It is shown that particles having a size of about 250 nm particles having a size of about 1 m are mixed and that 99% of entire powder particles have a particle size equal to or less than 2.4 m.

Embodiment 2

(40) According to the process order of FIG. 1, CeO.sub.2 powder, B.sub.2O.sub.3 powder, and MgH.sub.2 powder are mixed at a mole ratio of 1:3:11, the mixed powder is put in a high-speed steel vessel in an air atmosphere together with six 12.7-mm-diameter Cr steel balls and two 10-mm-diameter Cr steel balls at a weight ratio of about 1:39, and then high-energy ball milling is performed using a shaker mill for 2 hours. The milled powder is dispersed in acid-added ethanol and then deposited powder is collected.

(41) FIG. 5 is a graph showing X-ray diffraction patterns of the milled powder (1) and the powder (2) collected from the acidic solution. The X-ray diffraction pattern of the milled powder (1) shows that CeB.sub.6 and MgO are well synthesized due to chemical reaction using high-energy ball milling. The X-ray diffraction pattern of the powder (2) collected from the acidic solution shows that only pure CeB.sub.6 is well collected. Overall, the X-ray diffraction pattern of CeB.sub.6 does not greatly differ from that according to Embodiment 1.

Embodiment 3

(42) According to the process order of FIG. 1, CeO.sub.2 powder, B.sub.2O.sub.3 powder, and Mg powder are mixed at a mole ratio of 1:3:11, the mixed powder is put in a high-speed steel vessel in an air atmosphere together with six 12.7-mm-diameter Cr steel balls and two 10-mm-diameter Cr steel balls at a weight ratio of about 1:39, and then high-energy ball milling is performed using a shaker mill for 2 hours. The milled powder is dispersed in acid-added ethanol and then deposited powder is collected.

(43) FIG. 6 is a graph showing X-ray diffraction patterns of the milled powder (1) and the powder (2) collected from the acidic solution. The X-ray diffraction pattern of the milled powder (1) shows that CeB.sub.6 and MgO are well synthesized due to chemical reaction using high-energy ball milling. However, an X-ray diffraction pattern of iron (Fe) added due to wear and tear on the vessel and the balls during milling is additionally shown. The X-ray diffraction pattern of the powder (2) collected from the acidic solution shows that only pure CeB.sub.6 is well collected. Compared to FIGS. 2 and 5, it is shown that heights of peaks of CeB.sub.6 are increased and FWHM values thereof are reduced. This result means that CeB.sub.6 prepared according to Embodiment 3 has a crystal grain size greater than that of CeB.sub.6 prepared according to Embodiment 1 or 2.

(44) It is shown above that the cerium boride powder prepared using the CeO.sub.2 powder, the B.sub.2O.sub.3 powder, and the MgH.sub.2 powder has a crystal grain size much less than that of the cerium boride powder prepared using the CeO.sub.2 powder, the B.sub.2O.sub.3 powder, and the Mg powder, and a description thereof will now be provided.

(45) FIG. 7 shows a dark field image (a), a bright field image (b), a composition mapping image (c), and an electron diffraction pattern image (d) obtained by performing transmission electron microscopy (TEM) analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and MgH.sub.2 powder. Specifically, the cerium boride powder shown in FIG. 7 may be prepared using the above-described method according to Embodiment 2.

(46) Referring to FIG. 7, the dark field image shows that a cerium boride powder particle having a size of about 200 nm includes multiple Ce.sub.xB.sub.y crystal grains having a size of about 20 nm in average. The composition mapping image shows that all crystal grains are composed of cerium (Ce) and boron (B) and that a thin oxide layer is present on the surface of each crystal grain. The electron diffraction pattern image shows a ring pattern formed due to diffraction of a large number of very small crystal grains. The cerium boride powder including very small crystal grains is expected to exhibit excellent catalytic performance in the catalyst field due to a high specific surface area thereof.

(47) FIG. 8 shows a dark field image (a), a bright field image (b), a composition mapping image (c), and an electron diffraction pattern image (d) obtained by performing TEM analysis on cerium boride powder prepared using CeO.sub.2 powder, B.sub.2O.sub.3 powder, and Mg powder. Specifically, the cerium boride powder shown in FIG. 8 may be prepared using the above-described method according to Embodiment 2.

(48) Referring to FIG. 8, it is shown that a cerium boride powder particle having a size of about 220 nm includes a single Ce.sub.xB.sub.y crystal. The composition mapping image shows that the powder particle is composed of Ce and B and that a thin oxide layer is present on the surface of the powder particle. However, the electron diffraction pattern image does not show a ring pattern formed due to diffraction of a large number of very small crystal grains.

(49) As such, it is shown that the cerium boride powder prepared using the CeO.sub.2 powder, the B.sub.2O.sub.3 powder, and the MgH.sub.2 powder has a crystal grain size much less than that of and has a specific surface area much higher than that of the cerium boride powder prepared using the CeO.sub.2 powder, the B.sub.2O.sub.3 powder, and the Mg powder. It is expected that the higher specific surface area the cerium boride powder has, the better catalytic performance the cerium boride powder exhibits in the catalyst field.

(50) According to the afore-described various embodiments of the present invention, cerium boride powder having a particle size equal to or less than 5 m and a crystal grain size of 20 nm may be prepared at room temperature based on a simple and economical process by causing reaction between B.sub.2O.sub.3 powder, Mg or MgH.sub.2 powder, and CeCl.sub.3 or CeO.sub.2 powder at room temperature based on high-energy ball milling, and then removing by-products of reaction, e.g., MgO and MgCl.sub.2, by dissolving the by-products in an acidic solution. Particularly, compared to the Mg powder, the MgH.sub.2 powder may be used to prepare cerium boride powder having a smaller crystal grain size. However, the scope of the present invention is not limited to the above effects.

(51) While the present invention has been particularly shown and described with reference to embodiments thereof, it will be understood by one of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope of the present invention as defined by the following claims.