阅读说明：本技术 钡基钙钛矿陶瓷材料、其制备方法及应用 (Barium-based perovskite ceramic material, and preparation method and application thereof ) 是由 孙正 杨涛 刘文旭 李秋洋 畅丹阳 杜祖滟 谢拾一 于 2019-10-28 设计创作，主要内容包括：一种钡基钙钛矿陶瓷材料、其制备方法及应用,该制备方法包括将原料BaCO<Sub>3</Sub>、TiO<Sub>2</Sub>、ZrO<Sub>2</Sub>、GeO<Sub>2</Sub>按Ba(Zr<Sub>0.2</Sub>Ti<Sub>0.8-x</Sub>Ge<Sub>x</Sub>)O<Sub>3</Sub>的化学计量式摩尔比进行配料并预处理后预烧,其中x＝0.001至0.00175；将预烧后的原料与聚乙烯醇混合后研磨、烘干、过筛；将过筛后的物料制成坯体；将坯体烧结,即得到所述钡基钙钛矿陶瓷材料。本发明在保持Ba(Zr<Sub>0.2</Sub>Ti<Sub>0.8</Sub>)O<Sub>3</Sub>介质材料高介电常数的基础上,进一步降低材料的介电损耗,适应MLCC逐渐向小型化、低能耗方向发展的需要。(A barium-based perovskite ceramic material, a preparation method and applications thereof, wherein the preparation method comprises the step of using a raw material BaCO 3 、TiO 2 、ZrO 2 、GeO 2 According to Ba (Zr) 0.2 Ti 0.8‑x Ge x )O 3 The stoichiometric formula of (1) is prepared, pretreated and then presintered, wherein x is 0.001 to 0.00175; mixing the pre-sintered raw materials with polyvinyl alcohol, grinding, drying and sieving; preparing the sieved material into a green body; and sintering the blank to obtain the barium-based perovskite ceramic material. The invention keeps Ba (Zr) 0.2 Ti 0.8 )O 3 On the basis of high dielectric constant of the dielectric material, the dielectric loss of the material is further reduced, and the requirement that the MLCC gradually develops towards miniaturization and low energy consumption is met.)

1. A preparation method of a barium-based perovskite ceramic material comprises the following steps:

(1) mixing the raw material BaCO₃、TiO₂、ZrO₂、GeO₂According to Ba (Zr)_0.2Ti_0.8-xGe_x)O₃The stoichiometric formula of (1) is prepared, pretreated and then presintered, wherein x is 0.001 to 0.00175;

(2) mixing the pre-sintered raw materials with polyvinyl alcohol, grinding, drying and sieving;

(3) preparing the material sieved in the step (2) into a green body;

(4) and sintering the blank to obtain the barium-based perovskite ceramic material.

2. The production method according to claim 1,

the pre-sintering step in the step (1) comprises the steps of putting the raw materials into a medium-temperature furnace, and pre-sintering for 2 to 6 hours at the temperature of 1000 to 1100 ℃.

3. The production method according to claim 1,

the pretreatment step in step (1) comprises:

putting the raw materials into a polyester tank, adding deionized water and zirconia balls, carrying out ball milling for 4-8 hours, drying the ball-milled raw materials at 100-120 ℃, and sieving the dried raw materials with a 40-60-mesh sieve to obtain the pretreated raw materials.

4. The production method according to claim 1,

the total mass ratio of the polyvinyl alcohol to the raw material in the step (2) is 0.5 wt% to 1 wt%.

5. The production method according to claim 1,

the grinding time in the step (2) is 12 to 14 hours;

the drying temperature in the step (2) is 100 to 120 ℃.

6. The production method according to claim 1,

the mesh number of the sieve in the sieving step in the step (2) is 80 to 100 meshes.

7. The production method according to claim 1,

the diameter of the blank in the step (3) is 10-15 mm, and the thickness of the blank is 0.8-1 mm;

and (3) the preparation method of the green body comprises the step of pressing the material sieved in the step (2) into the green body by using a powder tablet press under the pressure of 2-6 MPa.

8. The production method according to claim 1,

the sintering temperature in the step (4) is 1300-1350 ℃, and the sintering time is 4 hours.

9. A barium-based perovskite ceramic material obtained by the production method as claimed in any one of claims 1 to 8,

the barium-based perovskite ceramic material has a room temperature dielectric constant of 9357 to 11220 and a dielectric loss of 0.001 to 0.003 when tested at a frequency of 1 kHz.

10. Use of the barium-based perovskite ceramic material as claimed in claim 9 in the field of multilayer chip ceramic capacitors.

Technical Field

The invention belongs to the field of ceramic materials, and particularly relates to a barium-based perovskite ceramic material, and a preparation method and application thereof.

Background

With the development of electronic equipment towards miniaturization, informatization and high intelligence, the requirements of miniaturization, integration and low energy consumption are also put forward for electronic components. A Multi-layer ceramic chip capacitor (MLCC) is a chip capacitor suitable for Surface mounting of Surface Mount Technology (SMT), and has a wide application in electronic products such as the internet, mobile communication devices, computers, digital cameras, smart phones, new-generation digital home appliances, and the like, and therefore, it is very important to reduce the size of the MLCC and reduce the power consumption of the MLCC to achieve the miniaturization and low energy consumption of electronic devices and electronic equipment.

Barium zirconate titanate (Ba (Zr)_0.2Ti_0.8)O₃) The ceramic material has high dielectric constant and moderate dielectric loss, has wide application prospect in MLCC, and needs to further reduce the dielectric loss on the basis of keeping the high dielectric constant in order to adapt to the development trend of miniaturization and low loss of the MLCC.

Disclosure of Invention

In view of the above, one of the main objects of the present invention is to provide a barium-based perovskite ceramic material, a preparation method and applications thereof, which are intended to at least partially solve at least one of the above technical problems.

In order to achieve the above object, as one aspect of the present invention, there is provided a method for preparing a barium-based perovskite ceramic material, comprising the steps of:

(1) mixing the raw material BaCO₃、TiO₂、ZrO₂、GeO₂According to Ba (Zr)_0.2Ti_0.8-xGe_x)O₃The stoichiometric formula of (1) is prepared, pretreated and then presintered, wherein x is 0.001 to 0.00175;

(2) mixing the pre-sintered raw materials with polyvinyl alcohol, grinding, drying and sieving;

(3) preparing the material sieved in the step (2) into a green body;

(4) and sintering the blank to obtain the barium-based perovskite ceramic material.

As another aspect of the invention, a barium-based perovskite ceramic material is also provided, which is obtained by the preparation method.

As a further aspect of the present invention, there is also provided a use of the barium-based perovskite ceramic material as described above in the field of multilayer chip ceramic capacitors.

Based on the technical scheme, compared with the prior art, the barium-based perovskite ceramic material, the preparation method and the application thereof have at least one of the following advantages:

1. the invention keeps Ba (Zr)_0.2Ti_0.8)O₃On the basis of high dielectric constant of the dielectric material, the dielectric loss of the material is further reduced, and the requirement that the MLCC gradually develops towards miniaturization and low energy consumption is met;

2. the invention prepares high dielectric constant low dielectric loss ceramic material Ba (Zr) for MLCC by a solid phase method_0.2Ti_0.8-xGe_x)O₃(x is 0.001 to 0.00175). Measured at a frequency of 1kHz, and has a dielectric constant ε at room temperature_r9357 to 11220, and a dielectric loss of 0.001 to 0.003.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.

The invention discloses a preparation method of a barium-based perovskite ceramic material, which comprises the following steps:

(1) mixing the raw material BaCO₃、TiO₂、ZrO₂、GeO₂According to Ba (Zr)_0.2Ti_0.8-xGe_x)O₃The stoichiometric formula of (1) is prepared, pretreated and then presintered, wherein x is 0.001 to 0.00175;

(2) mixing the pre-sintered raw materials with polyvinyl alcohol, grinding, drying and sieving;

(3) preparing the material sieved in the step (2) into a green body;

(4) and sintering the blank to obtain the barium-based perovskite ceramic material.

The pre-sintering step in the step (1) comprises the steps of putting the raw materials into a medium-temperature furnace, and pre-sintering for 2 to 6 hours at the temperature of 1000 to 1100 ℃.

Wherein the pretreatment step in step (1) comprises:

putting the raw materials into a polyester tank, adding deionized water and zirconia balls, carrying out ball milling for 4-8 hours, drying the ball-milled raw materials at 100-120 ℃, and sieving the dried raw materials with a 40-60-mesh sieve to obtain the pretreated raw materials.

Wherein the total mass ratio of the polyvinyl alcohol to the raw material in the step (2) is 0.5 wt% to 1 wt%.

Wherein the grinding time in the step (2) is 12 to 14 hours;

the drying temperature in the step (2) is 100 to 120 ℃.

Wherein, the mesh number of the sieve in the sieving step in the step (2) is 80 to 100 meshes.

Wherein the blank in the step (3) has a diameter of 10 to 15mm and a thickness of 0.8 to 1 mm;

and (3) the preparation method of the green body comprises the step of pressing the material sieved in the step (2) into the green body by using a powder tablet press under the pressure of 2-6 MPa.

Wherein the sintering temperature in the step (4) is 1300-1350 ℃, and the sintering time is 4 hours.

The invention also discloses a barium-based perovskite ceramic material which is obtained by adopting the preparation method;

the barium-based perovskite ceramic material is tested at the frequency of 1kHz, the room-temperature dielectric constant is 9357-11220, and the dielectric loss is 0.001-0.003.

The invention also discloses application of the barium-based perovskite ceramic material in the field of multilayer chip ceramic capacitors.

In one exemplary embodiment, the high dielectric constant low dielectric loss barium-based perovskite of the present inventionA mineral ceramic material having the chemical formula: ba (Zr)_0.2Ti_0.8-xGe_x)O₃Wherein x is 0.001-0.00175;

the preparation method of the ceramic material comprises the following specific steps:

(1) mixing BaCO₃、TiO₂、ZrO₂、GeO₂In stoichiometric formula Ba (Zr)_0.2Ti_0.8-xGe_x)O₃(wherein x is 0.001-0.00175), burdening, putting the powder raw materials into a polyester tank, adding deionized water and zirconia balls, and ball-milling for 4-8 hours;

(2) putting the ball-milled raw materials in the step (1) into a drying oven, drying at 100-120 ℃, and then sieving with a 40-mesh sieve;

(3) putting the dried and sieved powder raw material in the step (2) into a medium-temperature furnace, pre-sintering at 1000-1100 ℃, and preserving heat for 2-6 hours;

(4) mixing the pre-sintered powder raw material in the step (3) with PVA (polyvinyl alcohol), putting the mixture into a ball milling tank, adding zirconia balls and deionized water, carrying out ball milling for 10-14 hours, drying the mixture, sieving the dried mixture by using an 80-mesh sieve, and pressing the dried mixture by using a powder tablet press at the pressure of 2-6 MPa to form a blank; wherein the mass of the PVA is 0.5 percent of the total mass of the raw materials

(5) And (4) sintering the green body obtained in the step (4) at 1300-1325 ℃, and preserving heat for 2-6 hours to prepare the high-dielectric-constant low-dielectric-loss ceramic material for the MLCC.

Wherein, the diameter of the green body in the step (4) is 10mm, and the thickness is 1 mm.

Wherein the forming pressure of the blank body in the step (4) is 2-6 MPa, such as 4 MPa.

Wherein the sintering temperature of the step (5) is 1325 ℃.

Wherein said step (4) x is 0.0015.

The technical solution of the present invention is further illustrated by the following specific examples. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.

The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.

BaCO is used in the following examples₃(analytically pure), TiO₂(analytical grade), ZrO₂(analytically pure), GeO₂(super pure) is used as an initial raw material, and the dielectric ceramic material for the MLCC is prepared by a solid phase method.