KR20150063733A - Manufacturing method of barium titanate nano particles - Google Patents
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- KR20150063733A KR20150063733A KR1020130148456A KR20130148456A KR20150063733A KR 20150063733 A KR20150063733 A KR 20150063733A KR 1020130148456 A KR1020130148456 A KR 1020130148456A KR 20130148456 A KR20130148456 A KR 20130148456A KR 20150063733 A KR20150063733 A KR 20150063733A
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Abstract
Description
The present invention relates to a method for producing barium titanate nanoparticles, and more particularly to a method for producing BaTiO 3 To a production method capable of obtaining a powder.
Multilayer ceramic capacitors ("MLCCs"), which account for more than 70% of the total capacitor market, are an essential general purpose passive component used in all electronic products.
Recently, ultra-thin layer and ultra-high layering techniques of MLCC dielectric layers have been developed in accordance with the trend toward miniaturization and integration of parts, and in particular, a high dielectric constant of the dielectric is a key factor in this. That is, when the small BaTiO 3 particles are used, the number of particles in the thin dielectric layer increases, thereby forming a stable dielectric layer. In addition, the surface roughness of the sheet surface is improved according to the size of the particles, It is possible to prevent deterioration of the insulation property caused by the etching.
Accordingly, a technique is required to create a representative composition of the barium titanate (BaTiO 3) having a specific dielectric composition than using particles of small size and increase the dielectric constant by addition of sintering additives. However, since these sintering additives are added in small amounts and have various compositions, it is preferable that the particle size of the sintering additives is smaller than that of the BaTiO 3 particles as the base material, for example, nano-sized particles of 200 nm or less Do. Thus, a liquid-phase coating method for coating various additives on the surface of the base BaTiO 3 particles has been developed for such uniform addition.
Fig. 1 is a schematic diagram for conceptually illustrating such a liquid coating method. Is 1, the sintered by the addition of various additives such as Dy, Mn, Y, Mg in the base material BaTiO 3, resulting in a base material of BaTiO 3 being the core (core) additive adhered to the periphery of the core-shell called shell-shell structure in which the additive is coated on the surface of the base material by becoming a shell. These additive coatings can be attempted in a variety of ways. In general, additives are dissolved in a solvent, and BaTiO 3 powder having a nanoparticle size, which is a base material, is dispersed and then sprayed to a base material BaTiO 3 A method of causing the additive composition to precipitate on the particle surface is mainly used. Such a liquid coating method is disclosed in Korean Patent Laid-Open No. 10-2011-0003807 (published on Jan. 13, 2011), entitled " Additive-coated barium titanate composite powder and its preparation method, -2012-115834 (filed on October 18, 2012), each of which is incorporated herein by reference in its entirety, in "Method for producing barium titanate nano-particles".
On the other hand, the smallest BaTiO 3 particles that are currently applicable for mass production of the MLCC dielectric layer have an average particle size of only about 120 nm. As the particle size becomes smaller, a specific composition is prepared by changing the amount of various additives according to the amount of the additive, thereby obtaining the optimum characteristics of the reduced BaTiO 3 particle size.
However, in forming the MLCC dielectric layer, very small BaTiO 3 When the particles are applied, as the particle size decreases, BaTiO 3 There is a serious problem that the tetragonality of the particle structure is lowered and its dielectric constant is rapidly lowered. In addition, in order to manufacture and apply such nanoparticles, an increase in the manufacturing cost and an increase in the material cost due to an increase in the amount of the sintering additive required as the specific surface area increases. These nano BaTiO 3 Due to difficulties in mass production of particles and an increase in unit price, it is unclear whether BaTiO 3 having a size of 120 nm or less is currently applied. Therefore, when BaTiO 3 A new method of securing excellent dielectric constant and temperature stability should be sought while achieving the effect of using particles.
Accordingly, the present invention relates to BaTiO 3 And to provide a production method capable of obtaining a powder.
According to another aspect of the present invention, there is provided a method for preparing a barium titanate nano powder, comprising: mixing two or more barium titanate nano powders having different particle sizes with a metal element additive; Of barium titanate nano powder at the same time by mixing and drying the barium titanate nano powder. The method may further include mixing the first nanopowder having a barium titanate particle size of 120 to 250 nm and the second nanopowder having a size of 40 to 120 nm with a metal element additive, And the second nanopowder may be mixed and dried at the same time to produce barium titanate nano powder. The first nanopowder may include 30 to 70 wt% of the total amount of the first nanopowder and the second nanopowder, ≪ / RTI >
The metal element may be selected from the group consisting of Si, Mg, Mn, Cr, Dy, Y, Ca, La, Eu, Zr, Al and Ba. Based precursor, an acetate precursor, a chloride precursor, a nitride precursor, and a carbide precursor. The amount of the metal element additive may be 0.1 to 3 mol% of the barium titanate powder.
In addition, the mixing process may use a solvent that is at least one of ethanol, methanol, toluene, benzene, acetone, and distilled water.
In particular, at least one of a vacuum type paste mixer and a vacuum type paste mixer may be used for the mixing and drying at the same time.
According to the present invention, two or more barium titanate nano powders having different particle sizes are mixed with a metal element additive, respectively, and the two or more barium titanate nano powders thus coated are simultaneously mixed and dried to prepare barium titanate nano powder , BaTiO 3 improved in dielectric properties and temperature stability Powder can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram for conceptually illustrating a general method of coating a liquid phase of BaTiO 3. FIG.
FIG. 2 is a flow chart illustrating a method of coating and mixing BaTiO 3 nanocrystals having two different grain sizes (150 nm and 80 nm) according to an embodiment of the present invention to produce a final BaTiO 3 nano powder.
3 is a schematic diagram of a conventional vacuum paste mixer;
4A and 4B are electron micrographs of BaTiO 3 powder particles each coated with a metal element additive as an embodiment of the present invention, wherein FIG. 4A is a photograph of a 150 nm particle size BaTiO 3 powder and FIG. 4B is a photograph of a BaTiO 3 3 Photo of the powder.
5 is a graph showing the relationship between a particle size of 150 nm coated with a metal element additive (composition A: Dy 0.75 mol%, Mg 1.5 mol%, Mn 0.1 mol%, Cr 0.1 mol% and Si 0.65 mol%), Electron micrographs of sintered bodies obtained by sintering BaTiO 3 powders in a reducing atmosphere at 1200 ° C for 2 hours.
Figure 6 is a graph of the dielectric properties of the coated 150 nm particle size BaTiO 3 powder of Figure 5;
7a to 7c illustrate another embodiment of the present invention in which a metal element additive of various compositions (composition a contains 0.2 mol% of Mn, 0.75 mol% of Dy, 0.75 mol% of Si and 1.25 mol% of Mg, , Dy 0.75mol%, Si 1.0mol% and Mg 1.25mol%; and c is the composition Mn 0.2mol%, Dy 0.75mol%, Si 1.5mol% and 2.5mol% Mg) of particle size 80㎚ BaTiO 3 powder coated with Electron micrographs of each sintered body sintered in a reducing atmosphere at 1200 ° C for 2 hours.
8 is a graph of dielectric properties of each of the sintered bodies of FIGS. 7A to 7C.
Figure 9a ~ 9c is 150㎚ particle size of BaTiO 3 powder (Composition A) and the particle size of each 80㎚ BaTiO 3 powder (composition a ~ c) of FIG. 7a ~ 7c 50wt% of 5: co-mixed in a ratio of 50wt%, and Electron micrographs of each sintered body obtained by sintering the final BaTiO 3 powder obtained by drying at 1200 ° C. for 2 hours in a reducing atmosphere.
FIG. 10A is a graph of dielectric properties according to the compositions Aa, Ab, and Ac of FIGS. 9a to 9c, and FIG. 10b is a graph of temperature stability (TCC) according to each of these compositions.
The present inventors have studied how to overcome various limitations of nanotization of BaTiO 3 particles as described above, and have developed a method of mixing two or more BaTiO 3 nano powders having different particle sizes.
This sintering of a BaTiO 3 nano-powder mixture, BaTiO 3 particles of small size to be present between the BaTiO 3 particles of relatively large size to thereby it is possible to improve the surface roughness of the shaped dielectric sheet. Large-sized BaTiO 3 particles act as seeds in the microstructure, thereby suppressing the growth of particles as a whole and improving densification.
Also, generally relatively large BaTiO 3 nano particles are dielectric constant compared to the relatively small BaTiO 3 nano particles has a low high but the temperature stability, and relatively small BaTiO 3 nano particles relative to the relatively large BaTiO 3 nano particles permittivity By using these low-temperature but high-temperature tendency methods to mix these particles, BaTiO 3 The dielectric constant and temperature stability of the dielectric sheet formed of nanoparticles can be improved.
As described above, in the present invention, two or more BaTiO 3 powders having different particle sizes are mixed with each other before mixing with each other. And Ba, preferably at least one additive metal element selected from the group consisting of Si, Mg, Dy, Y, Mn, Ba, Ca and Cr.
Hereinafter, the present invention will be described with reference to various embodiments and examples, but the present invention is not limited thereto but is limited by the claims.
2 is a flow diagram illustrating a method for manufacturing a final BaTiO 3 nano-powder coatings and mixture of BaTiO 3 nano powders having two different particle size according to the embodiment of the present invention, in which the two nano-powder were 150 nm and 80 nm.
Referring to FIG. 2, as a first step, a coating solution of the metal element additive described above is prepared, and 150 nm particle size BaTiO 3 nano powder and 80 nm particle size BaTiO 3 nano powder are prepared, Coating with the metal element additive by simultaneous mixing with the coating solution and drying. As a second step, the two BaTiO 3 nano powders coated with the metal element additive are simultaneously mixed and dried to obtain a final BaTiO 3 nano powder.
For reference, the 150 nm particle size BaTiO 3 nano powder and the 80 nm particle size BaTiO 3 nano powder can be obtained by well-known manufacturing methods such as hydrothermal synthesis, precipitation, solid phase reaction and sol-gel method, For example, in Japanese Patent No. 1261497 (published on Mar. 5, 2013) of the present applicant.
According to the present invention, the mixing process can be performed using a solvent that is at least one of ethanol, methanol, toluene, benzene, acetone, and distilled water. Particularly, Drying is preferably carried out. That is, generally, in the mixing process, the amount of the solvent is reduced due to the evaporation or volatilization of the solvent over time, resulting in non-uniformity in the solution. Therefore, in the present invention, Thereby preventing the occurrence of additive non-uniformity in the solution due to the reduced amount of solvent. For this purpose, any known equipment capable of simultaneous mixing and drying, such as a conventional vacuum paste mixer, a pressure-sensitive paste mixer, or the like, shown as an example in FIG. 3, may be used in the present invention. This vacuum paste mixer or vacuum mixer is generally used as a mixed deaerator to mix and bubble removal without using an internal impeller in a conventional mixing equipment by using the centrifugal force, It is possible to remove even the pores of.
The metal element additive may be selected from the group consisting of Si, Mg, Mn, Cr, Dy, Y, Ca, La, Eu, Zr, Al and Ba, Mn, Ba, Ca and Cr. The amount of such additives to be added is preferably 0.1 to 3 mol% based on the BaTiO 3 powder. The precursors of these additives include oxide-based, acetate-based, chloride-based, nitride-based and carbide-based materials as shown in Table 1 below.
additive
The first and second steps according to the present invention as described above can be performed as the following process as one embodiment.
That is, first, a predetermined amount of Dy acetate is added to a beaker and distilled water is added to make the additives into a solution, followed by dissolving for 20 minutes using a magnetic bar. Then, the other ingredients of the additives and the ethanol are placed in another beaker, and the mixture is stirred for about 20 minutes using a magnetic bar to dissolve all of the ingredients of the additives. Then, a predetermined amount of 150 nm BaTiO 3 powder is put into a container for a paste-mixer, and Dy and the remaining additive solution, which are dissolved in a beaker, are added to the vessel. The container was placed in a paste mixer, coated and dried at 1600 rpm for 1 hour, and then subjected to a heat treatment for removing solvents and organic substances. The temperature was raised to 500 ° C at a heating rate of 2 ° C / minute and maintained at 500 ° C for 2 hours 5 ℃ / min and then cooled at a rate of coated BaTiO 3 Powder is obtained. Also, 80 nm BaTiO 3 powder is coated in the same manner as above. Then, the thus coated BaTiO 3 powders having different particle sizes are put into a paste mixer used in the first step, and are simultaneously mixed and dried at 1600 rpm for 30 minutes. Then, after the temperature is raised to 500 ℃ at a heating rate of 2 ℃ / minute for 2 hours in a 500 ℃ to remove the organic solvent and then cooled at a rate of 5 ℃ / min final BaTiO 3 Powder is obtained.
4A and 4B are electron micrographs of BaTiO 3 powder particles each coated with a metal element additive in the above-described manner as an embodiment of the present invention. FIG. 4A is a graph showing the particle size of 150 nm particle size BaTiO 3 powder, Represents an 80 nm particle size BaTiO 3 powder particle. At this time, also 150㎚ particle size of BaTiO 3 powder particles 4a is 0.75mol% Dy, 1.5mol% Mg, Mn 0.1mol%, 0.1mol%, and Cr was coated with a metal element additive consisting of Si 0.65mol%, of Figure 4b 80 nm particle size BaTiO 3 powder particles were coated with a metal element additive composed of 0.2 mol% of Mn, 0.75 mol% of Dy, 0.75 mol% of Si and 1.25 mol% of Mg.
Referring to FIGS. 4A and 4B, both the 150 nm particle size powder and the 80 nm particle size powder are relatively uniform in size and the aggregation between the particles is not so severe, so that the metal element additives appear uniformly added.
5 is an electron micrograph of a sintered product obtained by sintering a 150 nm particle-size BaTiO 3 powder coated with a metal element additive in a reducing atmosphere at 1200 ° C. for 2 hours in accordance with another embodiment of the present invention, Shows the dielectric properties of the coated 150 nm particle size BaTiO 3 powder of FIG. The composition of the metal element additive used in the coating was 0.75 mol% of Dy, 1.5 mol% of Mg, 0.1 mol% of Mn, 0.1 mol% of Cr and 0.65 mol% of Si,
(0.75 mol% of Dy, 1.5 mol% of Mg, 0.1 mol% of Mn, 0.1 mol% of Cr and 0.65 mol% of Si)
When the microstructure shown in Fig. 5 was observed, it was confirmed that a certain degree of densification was attained (density: 4.89 g / cm < 3 >) and grain growth was observed. Accordingly, as shown in FIG. 6, the dielectric constant shows a high dielectric constant of about 1900, but the temperature stability is low.
7a to 7c illustrate another embodiment of the present invention, in which 80 nm particle size BaTiO 3 powder coated with a metal element additive of various compositions is sintered for 2 hours in a reducing atmosphere at 1200 ° C., And Fig. 8 shows the dielectric properties of each of the sintered bodies of Figs. 7A to 7C. The metal element additive in Fig. 7A was composed of 0.2 mol% of Mn, 0.75 mol% of Dy, 0.75 mol% of Si and 1.25 mol% of Mg, and the metal element additive of 0.2 mol% of Mn, 0.75 mol% of Dy, 1.0 mol% and 1.25 mol% Mg, and the metal element additive in FIG. 7C is composed of 0.2 mol% of Mn, 0.75 mol% of Dy, 1.5 mol% of Si and 2.5 mol% of Mg and summarized in Table 3 :
(0.2 mol% of Mn, 0.75 mol% of Dy, 0.75 mol% of Si, and 1.25 mol% of Mg)
(Mn: 0.2 mol%, Dy: 0.75 mol%, Si: 1.0 mol%, Mg: 1.25 mol%
(0.2 mol% of Mn, 0.75 mol% of Dy, 1.5 mol% of Si, and 2.5 mol% of Mg)
7A to 7C, the composition of FIG. 7A shows that the grain structure of the microstructure is not yet densified (density: 3.86 g / cm 3 ), the composition of FIG. 7B is not densified : 4.35 g / cm 3 ). The grain of Fig. 7C showed a grain growth of approximately 300 nm, while the microstructure of the grain was grown to about 250 (density: 5.42 g / cm 3 ) It can be observed that the grain grows to a uniform size of ㎚. In this connection, referring to FIG. 8, it can be confirmed that the tendency of the densification and grain growth of the microstructure shown in FIGS. 7A to 7C agrees well with the tendency of the dielectric constant and the temperature stability. Particularly, That is, the temperature stability of the compositions a to c is much better than the temperature stability of the 150 nm particle size BaTiO 3 powder (that is, the composition A) shown in FIG. 8 shows that the dielectric constant of FIG. 7A is as low as about 1400, that of FIG. 7B is about 1800, and that of FIG. 7C is as high as about 2200.
On the basis of the results thus obtained, the 150 nm particle size BaTiO 3 powder (composition A) shown in Figs. 5 to 6 was mixed with the 80 nm particle size BaTiO 3 powder (composition a to c) of Figs. 7A to 7C and Fig. It is possible to obtain a BaTiO 3 nano powder satisfying high dielectric properties and temperature characteristics while sufficiently completing the densification, and it is also possible to obtain a BaTiO 3 nano powder having various dielectric properties and temperature Combinations of characteristics can be implemented.
Thus for an exemplary embodiment of the present invention, to Figure 9a ~ 9c is 150㎚ particle size of BaTiO 3 powder (Composition A) and each 80㎚ particle size BaTiO 3 powder of FIG. 7a ~ 7c (composition a ~ c) of Fig. 5 50wt%: an electron micrograph of each sintered product, sintering for 2 hours final BaTiO 3 powder obtained by co-mixing and dry to 50wt% ratio at 1200 ℃ reducing atmosphere. The compositions of FIGS. 9a-9c are summarized in Table 4 below:
9A to 9C, it can be seen that the sintered body of the composition Aa is sufficiently densified (density: 5.21 g / cm < 3 >) and exhibits a relatively uniform grain size, and the sintered body of the composition Ab has a slight grain growth (Density: 5.19 g / cm < 3 >). However, the sintered body of Composition Ac is densified (density: 5.18 g / cm 3 ), but the grain size is large and permittivity is high, but temperature stability is expected to be low. In conclusion, when the 150 nm particle size BaTiO 3 powder and the 80 nm particle size BaTiO 3 powder are mixed, the grain due to 150 nm grain and the grain due to 80 nm grain are mixed, It can be confirmed that the microstructure is exhibited.
Fig. 10A shows the dielectric characteristics according to the compositions A-a, A-b and A-c in Figs. 9A to 9C, and Fig. 10B shows the temperature coefficient of capacitance (TCC) according to the respective compositions.
10a to 10b, the composition A-a exhibits a high dielectric constant of about 1900 and satisfies the X7R condition, the composition A-b also has a high dielectric constant of about 2000, and the X7R condition is satisfied. On the other hand, the composition A-c has the highest dielectric constant of about 2100, but it is confirmed that the temperature stability does not satisfy the X7R condition.
As described above, according to the present invention, when the final BaTiO 3 powder mixed with 150 nm and 80 nm BaTiO 3 powders having different particle sizes are sintered and their microstructure is observed, it is possible to obtain a 150 nm BaTiO 3 powder particles are homogeneously mixed with 80 nm BaTiO 3 powder particles which are not densified, and serve as seeds of grain growth around these large particles, thereby suppressing grain growth but promoting densification Dielectric property and temperature stability are excellent.
In addition, the following Table 5 150㎚ BaTiO 3 powder particle size and composition of a ~ c each 80㎚ particle size BaTiO final BaTiO 3 powder obtained by mixing three powders in various mixing ratios 1200 ℃ reducing atmosphere is to be in the composition A after each two sintered in a dielectric property, and to a summary of temperature stability (TCC), in particular 80㎚ particle size of BaTiO 3 powder of composition a of 150㎚ particle size BaTiO 3 powder and the composition of a ~ c were measured 70wt% : 30 wt%, 60 wt%: 40 wt%, 50 wt%: 50 wt%, 40 wt%: 60 wt%, and 30 wt%: 70 wt%.
150㎚BaTiO 3 powder / 80㎚ BaTiO 3 powder
permittivity
TCC
Remarks
70/30 wt%
60/40 wt%
50/50 wt%
A + b: has X7R characteristic
40/60 wt%
A + b: has X6S character
30/70 wt%
A + b: has X7R characteristic
A + c: has X6S character
Table 5 shows that the mixing ratios of 60 wt%: 40 wt%, 50 wt%: 50 wt%, and 50 wt%, except for the composition in which the mixing ratio of the 150 nm particle size BaTiO 3 powder and the 80 nm particle size BaTiO 3 powder is 70/30
In addition, the following Table 5 other various particle sizes having BaTiO coating the three powders to each metal element additive together 50wt% of these BaTiO 3 powder: the final BaTiO 3 powder obtained by mixing 50wt% ratio at 1200 ℃ reducing atmosphere The dielectric properties and temperature stability (TCC) measured after sintering for 2 hours each are summarized as follows:
X particle size BaTiO 3 powder / Y particle size BaTiO 3 powder = 50/50 wt%
permittivity
TCC
Remarks
At this time, the various particle size BaTiO 3 powders of Table 6 were each coated with a metal element additive having the composition listed in Table 7 below:
Referring to Table 6, a mixture of each 120
In the above-described embodiments and examples of the present invention, the powder characteristics such as the average particle size, distribution and specific surface area of the composition powder, and the purity of the raw material, the amount of the impurity added, and the heat treatment conditions, It is quite natural for a person of ordinary skill in the field to have such a possibility.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the present invention and the advantages thereof, , Changes, additions, and the like are to be regarded as falling within the scope of the claims. For example, in the above-described embodiments and examples of the present invention, two BaTiO 3 nano powders having different particle sizes are used as samples. However, BaTiO 3 nano powders having different particle sizes used as a sample in the present invention The present invention can be embodied as a sample of BaTiO 3 nano powders having three or more different particle sizes from the contents of the present invention as long as those skilled in the art are familiar with the present invention. It is extremely self-evident. In the embodiments and examples of the present invention, BaTiO 3 nano powders having different particle sizes were simultaneously mixed and dried, and then sintered in a reducing atmosphere at 1200 ° C. However, the sintering temperature is not limited thereto. For example, 1250 < 0 > C. In addition, the reducing atmosphere was 3% H 2 + 97% N 2 mixed gas atmosphere.
Claims (14)
Mixing two or more barium titanate nano powders having different particle sizes with a metal element additive, respectively, and coating;
Comprising the step of preparing barium titanate nano powder by simultaneously mixing and drying the two or more coated barium titanate nano powders.
Mixing a first nanopowder having a barium titanate particle size of 120 to 250 nm and a second nanopowder having a size of 40 to 120 nm with a metal element additive;
And simultaneously mixing and drying the coated first nanopowder and the second nanopowder to prepare barium titanate nano-powder.
Wherein the metal element is at least one selected from the group consisting of Si, Mg, Mn, Cr, Dy, Y, Ca, La, Eu, Zr, Al and Ba.
Wherein the mixing is performed using a solvent which is at least one of ethanol, methanol, toluene, benzene, acetone and distilled water.
Wherein the step of mixing and drying simultaneously uses at least one of a vacuum type paste mixer and a vacuum type paste mixer.
Wherein the metal element additive is at least one of an oxide precursor, an acetate precursor, a chloride precursor, a nitride precursor and a carbide precursor of the metal element.
Wherein the amount of the metal element additive is 0.1 to 3 mol% based on the barium titanate powder.
Wherein the first nanopowder is mixed in an amount of 30 to 70 wt% based on the total amount of the first nanopowder and the second nanopowder.
The oxide-based precursor SiO 2, MgO, Mn 3 O 4, Dy 2 O 3, Cr 2 O 3, Y 2 O 3, V 2 O 5, ZrO 2, CaO, La 2 O 3, Eu 2 O 3 , Al 2 O 3, and BaO.
The acetate based precursor is (CH 3 COO) 3 La 2 O, (CH 3 CO 2) 3 Eu 2 O, C 2 H 5 O 4 Al, Al (OH) (C 2 H 3 O 2) 2, ( CH 3 CO 2) 32 O, (CH 3 CO 2) xZr (OH) y, CA (CH 3 COO) 22 O, C 6 H 9 DyO 62 O, Cr (CH 3 COO) 3, Mg (C 2 H 3 O 2) 22 O, Mn (CH 3 COO) 22 O, Si (O 2 C 2 H 5) 4, (CH 3 COO) 2 Ba, Ca (CH 3 COO) 2 · H 2 O, C 6 H 9 DyO 6 .xH 2 O, Mg (C 2 H 3 O 2 ) 2 .4H 2 O, and Mn (CH 3 COO) 2 .4H 2 O.
The chloride-based precursor CrCl 32 O, CrCl 3, MgCl 22 O, MgCl 2, MnCl 22 O, MnCl 2, DyCl 32 O, DyCl 3, SiCl 4, LaCl 32 O, LaCl 3, EuCl 32 O, EuCl 3 , AlCl 32 O, AlCl 3, YCl 32 O, YCl 3, ZrCL 4, ZrOCl 22 O, CaCl 22 O, CaCl 2, BaCl 2 · 2H 2 O, BaCl 2, CrCl 3 · xH 2 O, MgCl 2 · 6H 2 O, MnCl 2 .4H 2 O, DyCl 3 .H 2 O, YCl 3 .6H 2 O, CaCl 2 .2H 2 O and BaCl 2 .2H 2 O. .
The nitride-based precursor is Cr (NO 3) 22 O, Mg (NO 3) 22 O, Mn (NO 3) 22 O, Dy (NO 3) 32 O, LA (NO 3) 32 O, Eu (NO 3 ) 32 O, Al (NO 3 ) 32 O, Y (NO 3) 32 O, ZrO (NO 3) 22 O, Ca (NO 3) 22 O, Ba (NO 3) 2, Cr (NO 3) 2 · 9H 2 O, Mg (NO 3 ) 2 · 6H 2 O, Mn (NO 3) 2 · 6H 2 O, Dy (NO 3) 3 · 5H 2 O, Y (NO 3) 3 · 6H 2 O and Ca ( NO < 3 >) 2 xH2O. ≪ / RTI >
The carbide precursor may be selected from the group consisting of SiC, MgCO 3 , MnCO 3 , CrC 2 , Dy 2 (CO 3 ) 3 , Y 2 (CO 3 ) 3 .H 2 O, YC 2 , CaC 2 , CaCO 3 , La 2 ) 3 , ZrC, Al 4 C 3 and BaCO 3 .
Wherein the step of mixing and coating with the metal element additive and the step of preparing the barium titanate nano powder include a heat treatment for removing the solvent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112863869A (en) * | 2019-11-27 | 2021-05-28 | 三星电机株式会社 | Method for producing core-shell particles and multilayer ceramic electronic component |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112863869A (en) * | 2019-11-27 | 2021-05-28 | 三星电机株式会社 | Method for producing core-shell particles and multilayer ceramic electronic component |
| KR20210065529A (en) * | 2019-11-27 | 2021-06-04 | 삼성전기주식회사 | Manufacturing method of core-shell particle and multi-layer ceramic electronic parts including core-shell particle |
| US11538630B2 (en) | 2019-11-27 | 2022-12-27 | Samsung Electro-Mechanics Co., Ltd. | Method of producing core-shell particles and multilayer ceramic electronic component including core-shell particles |
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