KR102200476B1 - Method for manufacturing lead zirconate titanate powder - Google Patents

Abstract

The present invention relates to a method for producing lead zirconate titanate (PZT) powder, and more specifically, lead zirconate titanate (PZT) by mixing zirconium oxide, titanium oxide, lead oxide, first and second solvents, and water. A mixing step in which a precursor solution is prepared; A drying step in which the precursor solution is dried to produce lead zirconate titanate (PZT) precursor material; A pyrolysis step in which the precursor material is heated to pyrolyze; A milling step in which the pyrolyzed precursor material is milled to prepare a precursor powder; And a crystallization step in which lead zirconate titanate (PZT) powder is prepared by reheating and crystallizing the precursor powder. Includes.

Description

Manufacturing method of lead zirconate titanate (PZT) powder {METHOD FOR MANUFACTURING LEAD ZIRCONATE TITANATE POWDER}

The present invention relates to a method for producing lead zirconate titanate (PZT) powder, and more particularly, by drying, pyrolysis, milling, and crystallization of a precursor solution of lead zirconate titanate (PZT) mixed in a stoichiometric composition ratio. (PZT) relates to a method for producing powder.

A piezoelectric effect element is a material that exhibits a piezoelectric effect in which electrical energy and mechanical energy are mutually converted, and more specifically, changes in shape such as expansion and contraction when a voltage (electrical energy) is applied (mechanical energy). Is a material that generates voltage (electrical energy) when external force (mechanical energy) is applied. Such piezoelectric elements are widely used in various industrial fields such as various sensors, igniters of gas equipment, and piezoelectric transformers, and in particular, are used as core basic materials in the field of ultrasonic applications.

On the other hand, titanate zirconate year ((Pb (Zr, Ti) O _3, PZT), since titanate year (PbZrO _3), and titanate, open (as solid solutions of PbTiO _3), a high dielectric constant, has a high stability at a high temperature, Such lead zirconate titanate (PZT) has been mainly produced by a hydrothermal synthesis method in which a chemical reaction proceeds under high temperature and high pressure, or a dry method in which raw material powder is mixed and then sintered at a high temperature. In the case of, it takes a long time to perform processes such as charging of raw materials into the interior of the reactor, chemical reactions, and discharge of products, resulting in reduced production efficiency. Likewise, in the case of the dry method, since the raw material powder is sintered at a high temperature, there is a disadvantage in that the manufacturing cost is increased.

Korean Registered Patent Publication No. 10-0586086 (Name: Preparation of PZT nano powder using a continuous hydrothermal synthesis reactor) Republic of Korea Patent Publication No. 10-1722391 (Name: manufacturing method of lead zirconate titanate-based sintered body, lead zirconate titanate-based sintered body and lead zirconate titanate-based sputtering target)

The present invention is to solve the problems caused by the prior art as described above, and an object of the present invention is to more efficiently produce lead zirconate titanate (PZT) powder.

One aspect of a method for producing lead zirconate titanate (PZT) powder according to an embodiment of the present invention for achieving the above object is a mixture of zirconium oxide, titanium oxide, lead oxide, first and second solvents, and water. A mixing step in which lead zirconate (PZT) precursor solution is prepared; A drying step in which the precursor solution is dried to produce lead zirconate titanate (PZT) precursor material; A pyrolysis step in which the precursor material is heated to pyrolyze; A milling step in which the pyrolyzed precursor material is milled to prepare a precursor powder; And a crystallization step in which lead zirconate titanate (PZT) powder is prepared by reheating and crystallizing the precursor powder. Includes.

In addition, the mixing step may be performed at a temperature of 70°C.

In addition, the mixing step, wherein the zirconium oxide (l) and titanium oxide (l) are stirred and mixed at a preset temperature to prepare a mixed solution, a first mixing step; A step of adding a first solvent in which the first solvent is added to the mixed solution; Adding a second solvent in which the second solvent and water are added to the mixed solution; And a second mixing step in which the lead oxide (l) is mixed with the mixed solution. It may further include.

And, in the first solvent addition step, the second solvent addition step, and the second mixing step, the first and second solvents and water are in a volume ratio of the first solvent: the second solvent: water = 1:0.33:0.33. It may be added, and the molar concentration of zirconium, titanium, and lead in the precursor solution may be 0.3M.

In addition, in the mixing step, the zirconium oxide is zirconium propoxide (Zr(OCH ₂ CH ₂ CH ₃ ) ₄ ), and the titanium oxide is titanium isopropoxide, Ti[OCH (CH ₃ ) ₂ ] ₄ ), and the lead oxide may be lead acetate trihydrate (Pb(CH ₃ CO ₂ ) ₂ · 3H ₂ O).

And, in the mixing step, the first solvent may be acetic acid, and the second solvent may be propanol.

In addition, in the mixing step, the zirconium oxide, titanium oxide, and lead oxide may be mixed so that the stoichiometric composition ratio in the precursor solution is zirconium:titanium:lead=0.52:0.48:1.1.

Further, in the pyrolysis step, the dried precursor solution may be pyrolyzed at 300°C.

In addition, in the crystallization step, the milled powder may be crystallized at 600°C.

One aspect of a method for manufacturing lead zirconate titanate (PZT) powder according to an embodiment of the present invention for achieving the above object is, in the method for manufacturing lead zirconate titanate (PZT) powder: zirconium oxide (l) and titanium oxide To the solution in which (l) is mixed, a second solvent and water are added after the first solvent is added, and lead oxide (l) is additionally added to prepare a precursor solution, and the precursor solution is dried and pyrolyzed to prepare a precursor. Including a method for producing lead zirconate titanate (PZT) powder, characterized in that a material is produced, the precursor material is milled to prepare a precursor powder, and the precursor powder is crystallized to produce lead zirconate titanate (PZT) powder. do.

In addition, the precursor solution may be prepared at 70°C.

In addition, the zirconium oxide is zirconium propoxide (Zr(OCH ₂ CH ₂ CH ₃ ) ₄ ), and the titanium oxide is titanium isopropoxide, Ti[OCH(CH ₃ ) ₂ ] ₄ ), and the lead oxide may be lead acetate trihydrate (Pb(CH ₃ CO ₂ ) ₂ · 3H ₂ O).

In addition, the zirconium oxide, titanium oxide, and lead oxide may be mixed so that the stoichiometric composition ratio in the precursor solution is zirconium:titanium:lead=0.52:0.48:1.1.

In addition, the first solvent may be acetic acid, and the second solvent may be propanol.

In addition, the first and second solvents and water are added in a volume ratio of the first solvent: the second solvent: water = 1:0.33:0.33, and the molar concentration of zirconium, titanium, and lead in the precursor solution is 0.3M. Can be added.

In addition, the precursor material may be pyrolyzed at 300°C.

In addition, the precursor powder may be crystallized at 600°C.

In the method for producing lead zirconate titanate (PZT) powder according to an embodiment of the present invention, lead zirconate titanate (PZT) is prepared through a process of drying, pyrolysis, milling, and crystallizing a lead zirconate titanate (PZT) precursor solution. . At this time, since the pyrolysis and crystallization process is performed at a lower temperature than in the prior art, lead zirconate titanate (PZT) powder can be produced more efficiently.

1 is a flow chart showing a method for producing lead zirconate titanate (PZT) powder according to an embodiment of the present invention.
2 to 8 are photographs showing X-ray diffraction (XRD) results of lead zirconate titanate (PZT) powder prepared according to Preparation Examples and Comparative Examples 1 to 6 of the present invention.

Hereinafter, a method for producing lead zirconate titanate (PZT) powder will be described in more detail with reference to the accompanying drawings.

1 is a flow chart showing a method for producing lead zirconate titanate (PZT) powder according to an embodiment of the present invention.

Referring to FIG. 1, a method for producing lead zirconate titanate (PZT) powder according to the present embodiment includes a mixing step (S100) in which a precursor solution is prepared; A drying step in which the precursor solution is dried to generate a precursor material (S200); A pyrolysis step (S300) in which the precursor material is pyrolyzed; A milling step (S400) in which the pyrolyzed precursor material is milled to prepare a precursor powder; And a crystallization step (S500) in which the precursor powder is crystallized to prepare the lead zirconate titanate (PZT) powder. Includes.

More specifically, in the mixing step (S100), zirconium oxide (l), titanium oxide (l), lead oxide (l), first and second solvents, and water are mixed, and lead zirconate titanate (PZT) precursor The solution is prepared. And, the mixing step (S100), the first mixing step (S110); The first solvent addition step (S120); Adding a second solvent (S130); And a second mixing step (S140). It includes more.

And, in the mixing step (S100), the zirconium oxide, zirconium propoxide (zirconium propoxide, Zr (OCH ₂ CH ₂ CH ₃ ) ₄ ), the titanium oxide, titanium isopropoxide (titanium isopropoxide, Ti[OCH(CH ₃ ) ₂ ] ₄ ), and the lead oxide is lead acetate trihydrate (Pb(CH ₃ CO ₂ ) ₂ · 3H ₂ O), and the zirconium oxide, titanium oxide and lead oxide are , It may be mixed so that the stoichiometric composition ratio (mol) of zirconium, titanium and lead in the precursor solution is 0.52:0.48:1 to 1.1. In addition, in the mixing step (S100), the first solvent is acetic acid, the second solvent is propanol, and the first and second solvents and water are the first solvent: The second solvent:water may be added in a volume ratio of 1:0.33:0.33, and may be added so that the molar concentration of zirconium, titanium, and lead in the precursor solution is 0.3M. In addition, the first mixing step (S110) to the second mixing step (S140) may be performed at a temperature of 70°C.

More specifically, in the first mixing step (S110), zirconium oxide and titanium oxide are stirred and mixed at a preset temperature. For example, in the first mixing step (S110), 7.6 g of zirconium propoxide and 4.18 g of titanium isopropoxide may be stirred and mixed at 70° C. by a macroscopic bar.

Next, in the first solvent adding step (S120), the first solvent is added to the mixed solution prepared in the first mixing step (S110). For example, in the step of adding the first solvent (S120), 200 ml of acetic acid may be added to the mixed solution as the first solvent.

In addition, in the second solvent adding step (S130), the second solvent and water are added to the solution prepared in the first solvent adding step (S120). For example, in the step of adding the second solvent (S130), 66 ml of propanol and 66 ml of water may be added to the mixed solution as the second solvent.

Next, in the second mixing step (S140), lead oxide is mixed with the solution prepared in the second solvent adding step (S130). In the second mixing step (S140), the stoichiometric composition ratio of lead oxide to zirconium and titanium is 1 in preparation for the volatilization of lead in the pyrolysis step (S300) and crystallization step (S500) performed by heating as described later. A value exceeding, as described above, a stoichiometric composition ratio of 1.1, 14.16 g of lead acetate (lead acetate trihydrate, Pb(CH ₃ CO ₂ ) ₂ · 3H ₂ O) is the second solvent addition step (S130) By mixing in the mixed solution prepared in, finally lead zirconate titanate (PZT) precursor solution may be prepared.

In addition, in the drying step (S200), the precursor solution prepared in the mixing step (S100) is dried to generate a lead zirconate titanate (PZT) precursor material. For example, in the drying step (S200), the precursor solution is dried at 90° C. for 24 hours, so that lead zircoate titanate (PZT) precursor material may be produced.

In addition, in the pyrolysis step (S300), the precursor material generated in the drying step (S200) is heated and pyrolyzed. For example, in the pyrolysis step (S300), the precursor material may be heated from room temperature to 300°C at a temperature increase rate of 2.3°C/min, and may be pyrolyzed at 300°C for 100 minutes.

Further, in the milling step (S400), the precursor material pyrolyzed in the pyrolysis step (S300) is milled to prepare lead zirconate titanate (PZT) precursor powder. For example, in the milling step (S400), the pyrolyzed precursor solution may be pulverized by a general milling machine to prepare lead zirconate titanate (PZT) precursor powder.

Finally, in the crystallization step (S500), the precursor powder prepared in the milling step (S400) is reheated to crystallize, thereby finally producing lead zirconate titanate (PZT) powder. For example, in the crystallization step (S500), the milled precursor powder is heated from room temperature to 600°C at a temperature increase rate of 3.2°C/min and crystallized at 600°C for 10 minutes, thereby leading to lead zirconate titanate (PZT). Powders can be prepared.

Hereinafter, the present invention will be described in more detail by examples and experimental examples. These preparation examples are for illustrative purposes only, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited to these Examples and Experimental Examples.

Example

<Production Example>

In the preparation example, in the mixing step (S100), zirconium oxide, titanium oxide, lead oxide, first and second solvents, and water were mixed to prepare lead zirconate titanate (PZT) precursor solution. In this case, the first mixing step (S110) to the second mixing step (S140) to be described later were performed at 70°C.

More specifically, in the first mixing step (S110), 7.6 g of zirconium propoxide and 4.18 g of titanium isopropoxide were stirred and mixed by a macronetic bar.

Next, in the first solvent addition step (S120), 200 ml of acetic acid was added to the mixed solution prepared in the first mixing step (S110).

And, in the second solvent addition step (S130), 66 ml of propanol and water were added to the solution prepared in the first solvent addition step (S120), respectively.

In addition, in the second mixing step (S140), 14.16 g of lead acetate was added to the solution prepared in the second solvent addition step (S130) and mixed to prepare a precursor solution. At this time, the stoichiometric composition ratio of zirconium, titanium and lead in the prepared precursor solution satisfies 0.52:0.48:1.1, respectively, and the molar concentrations of zirconium, titanium and lead in the precursor solution were 0.3M.

And, in the drying step (S200), the precursor solution prepared in the precursor mixing step (S100) was dried for 24 hours at 90 ℃.

In addition, in the pyrolysis step (S300), the precursor solution dried in the drying step (S200) was heated to 300°C at a heating rate of 2.3°C/min, and pyrolyzed at 300°C for 100 minutes.

And, in the milling step (S400), the precursor solution pyrolyzed in the pyrolysis step (S300) was pulverized by a milling machine.

Finally, in the crystallization step (S500), the powder milled in the milling step (S400) is heated from room temperature to 600°C at a heating rate of 3.2°C/min, and crystallized at 600°C for 10 minutes, so that zirconic acid titanate Lead (PZT) powder was prepared.

<Comparative Example 1>

In Comparative Example 1, lead zirconate titanate (PZT) powder was prepared in the same manner as in Preparation Example, but in the first mixing step (S100), zirconium propoxide and titanium isopropoxide were stirred and mixed at 100°C. .

<Comparative Example 2>

In Comparative Example 2, lead zirconate titanate (PZT) powder was prepared in the same manner as in Preparation Example, but in the second solvent addition step (S130), 40 ml of propanol and water were added, respectively.

<Comparative Example 3>

In Comparative Example 3, lead zirconate titanate (PZT) powder was prepared in the same manner as in Preparation Example, but in the second solvent addition step (S130), 80 mL of propanol and water were added, respectively.

<Comparative Example 4>

In Comparative Example 4, lead zirconate titanate (PZT) powder was prepared in the same manner as in Preparation Example, but without the addition of propanol and water in the second solvent addition step (S120), only 200 ml of acetic acid was used as a solvent to lead zirconate titanate. A (PZT) precursor solution was prepared.

<Comparative Example 5>

In Comparative Example 5, a lead zirconate titanate (PZT) powder was prepared in the same manner as in Preparation Example, but without the addition of acetic acid in the first solvent addition step (S120) and propanol in the second solvent addition step (S130), 250 ml Only water of was used as a solvent to prepare a lead zirconate titanate (PZT) precursor solution.

<Comparative Example 6>

In Comparative Example 6, lead zirconate titanate (PZT) powder was prepared in the same manner as in Preparation Example, but the second mixing step (S140) was performed first, and acetic acid was added to Pb(CH3CO2)2 · 3H2O, and then propanol And zirconium propoxide and titanium isopropoxide were mixed in a solution to which water was added to prepare lead zirconate titanate (PZT) precursor solution.

Experimental example

XRD (X-ray Diffraction) analysis was performed on the lead zirconate titanate (PZT) powder prepared according to Preparation Examples and Comparative Examples 1 to 6, and graphs are attached to FIGS. 2 to 8.

Referring to FIG. 2, in the case of the preparation example, a sharp peak was observed around 30°. This is, in the case of the preparation example, that zirconium, titanium and lead reacted in a stoichiometric composition ratio of lead zirconate titanate (PZT), that is, zirconium: titanium: lead = 0.52: 0.48: 1, and lead zirconate titanate (PZT) was prepared. it means.

On the other hand, referring to Figs. 3 to 8, the peak around 30° was more dull than in Preparation Example, and additionally, the peak around 29° or 34° was observed. This means that impurities, such as pyrochloro phase (Pyrochlore), lead oxide (PbO), titanium dioxide (TiO ₂ ), and zirconium oxide (ZrO), were produced when preparing lead zirconate titanate (PZT). Therefore, compared to the Preparation Example, in Comparative Examples 1 to 6, it can be confirmed that impurities other than lead zirconate titanate (PZT) are generated.

Claims (17)

Zirconium oxide, titanium oxide, lead oxide, first and second solvents and water are mixed to prepare lead zirconate titanate (PZT) precursor solution, a mixing step (S100);
A drying step (S200) in which the precursor solution is dried to generate lead zirconate titanate (PZT) precursor material;
The precursor material is heated to pyrolyze, the pyrolysis step (S300);
The pyrolyzed precursor material is milled to prepare a precursor powder, a milling step (S400); And
Crystallization step (S500) in which lead zirconate titanate (PZT) powder is prepared by reheating the precursor powder to crystallize; Including
The mixing step (S100),
Zirconium oxide (l) and titanium oxide (l) are stirred and mixed at a preset temperature to prepare a mixed solution, a first mixing step (S110);
Adding the first solvent to the mixed solution (S120);
A second solvent addition step (S130) in which the second solvent and water are added to the mixed solution; And
A second mixing step (S140) in which lead oxide (l) is mixed with the mixed solution; Lead zirconate titanate (PZT) powder manufacturing method further comprising.
The method of claim 1,
The mixing step (S100) is a method for producing lead zirconate titanate (PZT) powder performed at a temperature of 70°C.
delete The method of claim 1,
In the first solvent addition step (S120), the second solvent addition step (S130), and the second mixing step (S140),
The first and second solvents and water are added in a volume ratio of the first solvent: the second solvent: water = 1:0.33:0.33, and the molar concentration of zirconium, titanium, and lead in the precursor solution is 0.3M. Lead zirconate titanate (PZT) powder manufacturing method.
The method according to any one of claims 1, 2 and 4,
In the mixing step (S100),
The zirconium oxide is zirconium propoxide (Zr(OCH ₂ CH ₂ CH ₃ ) ₄ ), and the titanium oxide is titanium isopropoxide, Ti[OCH(CH ₃ ) ₂ ] ₄ ), and the lead oxide is lead acetate trihydrate (Pb(CH ₃ CO ₂ ) ₂ · 3H ₂ O), lead zirconate titanate (PZT) powder manufacturing method.
The method according to any one of claims 1, 2 and 4,
In the mixing step (S100),
The first solvent is acetic acid, the second solvent is propanol, lead zirconate titanate (PZT) powder production method.
The method according to any one of claims 1, 2 and 4,
In the mixing step (S100),
The zirconium oxide, titanium oxide, and lead oxide are mixed so that the stoichiometric composition ratio in the precursor solution is zirconium: titanium: lead = 0.52:0.48:1.1 lead zirconate titanate (PZT) powder manufacturing method.
The method according to any one of claims 1, 2 and 4,
In the pyrolysis step (S300),
The dried precursor solution is a method for producing lead zirconate titanate (PZT) powder that is thermally decomposed at 300°C.
The method according to any one of claims 1, 2 and 4,
In the crystallization step (S500),
The milled powder is a lead zirconate titanate (PZT) powder that is crystallized at 600°C.
In the manufacturing method of lead zirconate titanate (PZT) powder:
To a solution in which zirconium oxide (l) and titanium oxide (l) are mixed, a second solvent and water are added after the first solvent is added, and lead oxide (l) is additionally added to prepare a precursor solution,
The precursor solution is dried and thermally decomposed to produce a precursor material,
The precursor material is milled to prepare a precursor powder,
Lead zirconate titanate (PZT) powder manufacturing method, characterized in that the precursor powder is crystallized to prepare lead zirconate titanate (PZT) powder.
The method of claim 10,
The precursor solution is a method for producing lead zirconate titanate (PZT) powder prepared at 70°C.
The method of claim 10 or 11,
The zirconium oxide is zirconium propoxide (Zr(OCH ₂ CH ₂ CH ₃ ) ₄ ), and the titanium oxide is titanium isopropoxide, Ti[OCH(CH ₃ ) ₂ ] ₄ ), and the lead oxide is lead acetate trihydrate (Pb(CH ₃ CO ₂ ) ₂ · 3H ₂ O), lead zirconate titanate (PZT) powder manufacturing method.
The method of claim 10 or 11,
The zirconium oxide, titanium oxide, and lead oxide are mixed so that the stoichiometric composition ratio in the precursor solution is zirconium: titanium: lead = 0.52:0.48:1.1 lead zirconate titanate (PZT) powder manufacturing method.
The method of claim 10 or 11,
The first solvent is acetic acid, the second solvent is propanol, lead zirconate titanate (PZT) powder production method.
The method of claim 10 or 11,
The first and second solvents and water are added in a volume ratio of the first solvent: the second solvent: water = 1:0.33:0.33, and are added so that the molar concentration of zirconium, titanium, and lead in the precursor solution is 0.3M. Lead zirconate titanate (PZT) powder manufacturing method.
The method of claim 10 or 11,
The precursor material is a method of producing lead zirconate titanate (PZT) powder that is thermally decomposed at 300°C.
The method of claim 10 or 11,
The precursor powder is a lead zirconate titanate (PZT) powder that is crystallized at 600°C.

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