阅读说明：本技术 一种低温烧结铌镍-锆钛酸铅压电陶瓷材料及其制备方法 (Low-temperature sintered niobium-nickel-lead zirconate titanate piezoelectric ceramic material and preparation method thereof ) 是由 尚勋忠 赵兵 周桃生 朱天文 吴静 尚银忠 于 2020-08-06 设计创作，主要内容包括：本发明公开了一种低温烧结铌镍-锆钛酸铅压电陶瓷材料及其制备方法,原料配方为:xPb(Ni<Sub>1/3</Sub>Ti<Sub>2/3</Sub>)O<Sub>3</Sub>-(1-x)Pb(Zr<Sub>y</Sub>Ti<Sub>1-y</Sub>)O<Sub>3</Sub>+awt.％(cPbO-dCuO),其中x＝0.34-0.36,y＝0.4-0.42,a＝0-2,c＝0.75-0.8,c+d＝1,本发明采用传统的固相烧结方法,具体的步骤包括配料球磨、预烧、然后粉碎、加入掺杂的PbO和CuO、细磨、加去离子水造粒、压片、烧结、烧银、极化。烧结温度过高,会导致PbO挥发,当加入少量的PbO和CuO后便可极大的降低烧结温度,实验结果表明,本发明的压电陶瓷的各项性能较好,其中压电常数d<Sub>33</Sub>为780PC/N,机电耦合系数kp达到0.62,室温介电常数<Image he="99" wi="167" file="DDA0002621622190000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>达到3982,室温介电损耗tanδ仅2.5％,且烧结温度≤1000℃,能够满足制备压电扬声器等器件的要求。(The invention discloses a low-temperature sintered niobium-nickel-lead zirconate titanate piezoelectric ceramic material and a preparation method thereof, wherein the formula of the raw material is xPb (Ni) 1/3 Ti 2/3 )O 3 ‑(1‑x)Pb(Zr y Ti 1‑y )O 3 + awt% (cPbO-dCuO), where x is 0.34-0.36, y is 0.4-0.42, a is 0-2, c is 0.75-0.8, and c + d is 1, and the invention adopts the traditional solid phase sintering method, and the concrete steps include batch ball milling, presintering, then crushing, adding doped PbO and CuO, fine grinding, adding deionized water for granulation, tabletting, sintering, silver firing, and polarization. The sintering temperature is too high, which can cause PbO volatilization, and the sintering temperature can be greatly reduced after a small amount of PbO and CuO are added, and experimental results show that the piezoelectric ceramic has good performances, wherein the piezoelectric constant d 33 780PC/N, an electromechanical coupling coefficient kp of 0.62, and a room-temperature dielectric constant 3982, the room temperature dielectric loss tan is only 2.5 percent, the sintering temperature is less than or equal to 1000 ℃, and the requirements for preparing devices such as piezoelectric speakers and the like can be met.)

1. The low-temperature sintered niobium-nickel-lead zirconate titanate piezoelectric ceramic material is characterized by comprising the following components in percentage by weight: xPb (Ni)_{1/ 3}Ti_2/3)O₃-(1-x)Pb(Zr_yTi_1-y)O₃+ awt% (cPbO-dCuO), where x ═ 0.34-0.36, y ═ 0.4-0.42, a ═ 0-2, c ═ 0.75-0.8, and c + d ═ 1.

2. A preparation method of a low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material is characterized by comprising the following steps:

step 1: adding Pb₃O₄、ZrO₂、TiO₂、Nb₂O₅NiO raw material is expressed as xPb (Ni)_1/3Ti_2/3)O₃-(1-x)Pb(Zr_yTi_1-y)O₃Proportioning according to a stoichiometric ratio, wherein x is 0.34-0.36, y is 0.4-0.42, uniformly mixing by wet ball milling, drying and presintering;

step 2: pulverizing the powder preburning in the step A, weighing, and according to awt%(cPbO-dCuO) weighing Pb₃O₄And mass of CuO, wherein the calculated PbO mass is converted to Pb₃O₄Adding the powder obtained by pre-sintering into the powder with the mass of a being 0-4, c being 0.75-0.8 and c + d being 1, and finely grinding. Then drying, granulating and pressing into a ceramic green body;

and step 3: and B, sintering the ceramic blank obtained in the step B, then loading an electrode, and polarizing.

3. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: pb in the above-mentioned step 1 and step 2₃O₄Purity greater than 98% ZrO₂Purity of more than 99.5 percent and TiO₂Purity greater than 99.8%, Nb₂O₅The purity is more than 99.99 percent, the NiO purity is more than 99 percent, and the CuO purity is more than 99 percent.

4. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: the dispersing agents in the step 1 and the step 2 are deionized water, and the ball milling rotating speed is 250r/min, wherein the ball milling time in the step 1 is 2 hours, and the fine milling time in the step 3 is 4 hours.

5. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: the drying temperature in the step 1 and the step 2 is both 100-130 ℃.

6. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: the pre-sintering in the step 1 is to keep the temperature at 800-900 ℃ for 2-3h, and the heating rate is 2-4 ℃/min.

7. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: in the step 2, awt% is a% of the mass of the powder left after pre-sintering, and c and d are molar ratios of PbO and CuO accounting for awt% (cpbO-dCuO), respectively.

8. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: and in the step 2, 5-10 wt.% of deionized water is added as a binder for granulation, the forming pressure in the step 2 is 2-4Mpa, and the pressure maintaining time is 10-20 s.

9. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: the sintering of the ceramic blank in the step 3 is to preserve heat for 3-5 hours at the temperature of 900-1000 ℃, and the heating rate is 2-4 ℃/min.

10. The method for preparing the low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material according to claim 2, wherein the method comprises the following steps: the polarization in the step 3 is polarization for 10-30min at 40-60 ℃ and 2-4 kv/mm.

Technical Field

The invention relates to the field of electronic information functional materials and components, in particular to a low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material and a preparation method thereof.

Background

The piezoceramic material serving as an important functional material for interconversion of mechanical energy and electric energy can be prepared into various shapes and material characteristics in any polarization direction due to stable chemical properties and excellent physical properties, is widely applied to various devices such as transducers, oscillators, sensors, filters and the like, and plays an indispensable role in the fields of daily life, industrial production and military.

Among the piezoelectric ceramic materials in practical use, lead-containing piezoelectric ceramics are dominant, but the sintering temperature is generally 1200-1300 ℃. Higher sintering temperatures result in:

1. since the melting point of PbO is 880 ℃, PbO volatilizes at high temperature, and the volatilization of PbO causes fluctuation and deviation from the composition design of the ceramic component on one hand, and the volatilization of PbO also causes serious environmental pollution on the other hand.

2. In the multilayer device, if the sintering temperature is too high, noble metals such as Pt and Pd with high melting points have to be used as the inner electrode to prevent the electrode from being oxidized during sintering, which increases the cost of the device.

3. Too high a sintering temperature leads to too high energy consumption.

Therefore, it is necessary to reduce the sintering temperature, and among the piezoelectric ceramic materials, the ternary system niobium nickel-lead zirconate titanate piezoelectric ceramic material (PZT-PNN) has the characteristic of 'soft material',has high electromechanical coupling coefficient Kp and piezoelectric constant d₃₃High dielectric constantAnd low dielectric loss tan, and the sintering temperature is relatively low and is relatively easy to reduce

Disclosure of Invention

The invention aims to provide a low-temperature sintered niobium-nickel-lead zirconate titanate piezoelectric ceramic material and a preparation method thereof, and aims to solve the problems of disordered composition ratio of ceramics, higher cost of internal electrodes of multilayer devices and high energy consumption caused by overhigh sintering temperature of the conventional piezoelectric ceramic in the background art.

In order to achieve the purpose, the invention provides the following technical scheme: a low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material comprises the following components in percentage by weight: xPb (Ni)_1/3Ti_2/3)O₃-(1-x)Pb(Zr_yTi_1-y)O₃+ awt% (cPbO-dCuO), where x ═ 0.34-0.36, y ═ 0.4-0.42, a ═ 0-2, c ═ 0.75-0.8, and c + d ═ 1.

A preparation method of a low-temperature sintered niobium nickel-lead zirconate titanate piezoelectric ceramic material comprises the following steps:

step 1: adding Pb₃O₄、ZrO₂、TiO₂、Nb₂O₅NiO raw material is expressed as xPb (Ni)_1/3Ti_2/3)O₃-(1-x)Pb(Zr_yTi_1-y)O₃Proportioning according to a stoichiometric ratio, wherein x is 0.34-0.36, y is 0.4-0.42, uniformly mixing by wet ball milling, drying and presintering;

step 2: b, crushing the powder subjected to the pre-sintering in the step A, weighing the powder, and weighing Pb according to awt% (cPPO-dCuO)₃O₄And mass of CuO, wherein the calculated PbO mass is converted to Pb₃O₄Adding the powder obtained by pre-sintering into the powder with the mass of a being 0-4, c being 0.75-0.8 and c + d being 1, and finely grinding. Then drying, granulating and pressing into a ceramic green body;

and step 3: and B, sintering the ceramic blank obtained in the step B, then loading an electrode, and polarizing.

Preferably, Pb in the step 1 and the step 2₃O₄Purity greater than 98% ZrO₂Purity of more than 99.5 percent and TiO₂Purity greater than 99.8%, Nb₂O₅The purity is more than 99.99 percent, the NiO purity is more than 99 percent, and the CuO purity is more than 99 percent.

Preferably, the dispersing agents in the step 1 and the step 2 are deionized water, and the ball milling rotation speed is 250r/min, wherein the ball milling time in the step 1 is 2 hours, and the fine milling time in the step 3 is 4 hours.

Preferably, the drying temperature in step 1 and step 2 is 100-.

Preferably, the pre-sintering in the step 1 is carried out at 800-900 ℃ for 2-3h, and the heating rate is 2-4 ℃/min.

Preferably, awt% in the step 2 is a% of the mass of the powder remaining after the pre-sintering, and c and d are molar ratios of PbO and CuO to awt% (cpbO-dCuO), respectively.

Preferably, the granulation in step 2 is to add 5 to 10 wt.% of deionized water as a binder, the forming pressure in step 2 is 2 to 4Mpa, and the dwell time is 10 to 20 s.

Preferably, the sintering of the ceramic body in the step 3 is carried out at the temperature of 900-1000 ℃ for 3-5 hours, and the heating rate is 2-4 ℃/min.

Preferably, the polarization in step 3 is polarization at 40-60 deg.C and 2-4kv/mm for 10-30 min.

Compared with the prior art, the invention has the beneficial effects that:

1. the optimal doping molar ratio of PbO and CuO is optimized, and whether the molar ratio of PbO and CuO corresponding to the optimal performance point is at a eutectic point or not is verified;

2. the small amount of low-temperature additive added is (PbO) Pb which is used by both CuO and Pb-based piezoelectric ceramics₃O₄The cost of the additive is low;

3. the sintering temperature can be reduced to 1000 ℃, the ceramic under low-temperature sintering has better piezoelectric and dielectric properties, wherein the piezoelectric constant d₃₃Can reach 780PC/N, the electromechanical coupling coefficient kp reaches 0.62, and the dielectric constant at room temperature

The dielectric loss tan at room temperature is only 2.5 percent, the Curie temperature Tc is relatively high and is about 220 ℃, the requirements of a multilayer chip structure piezoelectric ceramic device with higher piezoelectric coefficient and dielectric constant can be met, and the method has the advantages of simple process, low cost, easy large-scale production and the like.

Drawings

FIG. 1 is a graph showing piezoelectric constants d of niobium nickel-lead zirconate titanate piezoelectric ceramics prepared in examples 1 to 4₃₃And an electromechanical coupling coefficient kp map;

FIG. 2 is a graph showing the room temperature dielectric constants of the niobium nickel lead zirconate titanate piezoelectric ceramics prepared in examples 1 to 4

And a room temperature dielectric loss tan plot;

FIG. 3 is a full spectrum and a narrow spectrum of X-ray diffraction patterns of the niobium nickel lead zirconate titanate piezoelectric ceramics prepared in examples 1-4 and comparative example 2;

FIG. 4 is a graph showing the dielectric constant at 1kHz versus temperature curves of the niobium nickel lead zirconate titanate piezoelectric ceramics prepared in examples 1 to 4;

FIG. 5 is a graph showing the dielectric loss at 1kHz as a function of temperature for the niobium nickel lead zirconate titanate piezoelectric ceramics prepared in examples 1 to 5;

FIG. 6 is a graph showing the dielectric loss at 1kHz as a function of temperature for the niobium nickel-lead zirconate titanate piezoelectric ceramic prepared in comparative example 1;

FIG. 7 is a graph showing the dielectric loss at 1kHz as a function of temperature for the niobium nickel-lead zirconate titanate piezoelectric ceramic prepared in comparative example 1;

FIG. 8 is a phase diagram of PbO-CuO system in air.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.