CN111875374A - Low-temperature sintered niobium-nickel-lead zirconate titanate piezoelectric ceramic material and preparation method thereof - Google Patents
Low-temperature sintered niobium-nickel-lead zirconate titanate piezoelectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
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)1/3Ti2/3)O3‑(1‑x)Pb(ZryTi1‑y)O3+ 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 d33780PC/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.
Description
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 constant
And 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)1/3Ti2/3)O3-(1-x)Pb(ZryTi1-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)1/3Ti2/3)O3-(1-x)Pb(ZryTi1-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
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.
Example 1
The low temperature sintered niobium-nickel-lead zirconate titanate piezoelectric ceramic material and the preparation method thereof comprise the following steps:
step A: according to xPb (Ni)1/3Ti2/3)O3-(1-x)Pb(ZryTi1-y)O3Chemical formula (II) weighing Pb3O4、ZrO2、TiO2、Nb2O5Sequentially filling NiO raw material powder into a nylon ball milling tank, wherein x is 0.355 and y is 0.41, adding deionized water accounting for 60% of the mass of the raw materials, ball milling for 2 hours at the rotating speed of 250r/min, putting the uniformly mixed powder into an oven, and drying at 120 ℃;
and B: b, putting the dried powder obtained in the step A into an alumina crucible, and presintering in an atmosphere, wherein the presintering temperature is 850 ℃, the heat preservation time is 2 hours, and the heating rate is 4 ℃/min;
and C: b, grinding the pre-sintered block obtained in the step B, weighing the mass of the pre-sintered powder, calculating the mass of PbO and CuO of 1.5 wt.% of the mass of the pre-sintered powder according to 1.5 wt.% (0.76PbO-0.24CuO), and converting the mass into Pb3O4Weighing corresponding Pb3O4And CuO, the amount of Pb to be weighed3O4Adding CuO and presintering powder into a nylon ball milling tank, adding the presintering powder and adding Pb3O4And deionized water accounting for 60 percent of the total mass of CuO, ball-milling for 4 hours at the rotating speed of 250r/min, putting the powder mixed uniformly after ball-milling into an oven, and drying at 120 ℃;
step D: weighing the mass of the dried powder in the step C, grinding the dried powder, adding deionized water accounting for 6% of the mass of the dried powder in the step C, granulating, maintaining the pressure for 15s under the pressure of 4Mpa, and pressing into a blank;
step E: d, sintering the green body obtained in the step D in the atmosphere by adopting a powder embedding sintering method, wherein the sintering temperature is 1000 ℃, the heat preservation time is 4h, and the heating rate is 3 ℃/min;
step F: and E, applying an electrode to the piezoelectric ceramic piece obtained in the step E, and then polarizing in silicon oil, wherein the polarizing temperature is 40 ℃, the polarizing electric field is 3Kv/mm, and the polarizing time is 10 min.
FIGS. 1 and 2 contain the piezoelectric constant d of the niobium nickel-lead zirconate titanate piezoelectric ceramic obtained in example 133And electromechanical coupling coefficient kp, room temperature dielectric constant
And a room temperature dielectric loss tan, FIG. 3 contains a full XRD spectrum (2. theta.: 20-80 ℃ C.) and a narrow spectrum (2. theta.: 40-50 ℃ C.) of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 1, FIG. 4 contains a dielectric constant versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 1, and FIG. 5 contains a dielectric loss versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 1.
Example 2
This embodiment differs from embodiment 1 only in that: the molar ratios of PbO and CuO added after the pre-firing were 0.77 and 0.23, i.e., 1.5 wt.% (0.77PbO-0.23CuO), and the rest was the same as described in example 1.
FIGS. 1 and 2 contain the piezoelectric constant d of the niobium nickel-lead zirconate titanate piezoelectric ceramic obtained in example 233And electromechanical coupling coefficient kp, room temperature dielectric constant
And a room temperature dielectric loss tan, FIG. 3 contains a full XRD spectrum (2. theta.: 20-80 ℃ C.) and a narrow spectrum (2. theta.: 40-50 ℃ C.) of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 2, FIG. 4 contains a dielectric constant versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 2, and FIG. 5 contains a dielectric loss versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 2.
Example 3
This embodiment differs from embodiment 1 only in that: the molar ratios of PbO and CuO added after the pre-firing were 0.78 and 0.22, i.e., 1.5 wt.% (0.78PbO-0.22CuO), and the rest was the same as described in example 1.
FIGS. 1 and 2 contain the piezoelectric constant d of the niobium nickel-lead zirconate titanate piezoelectric ceramic obtained in example 333And an electromechanical coupling systemSeveral kp, dielectric constant at room temperature
And a room temperature dielectric loss tan, FIG. 3 contains a full XRD spectrum (2. theta.: 20-80 ℃ C.) and a narrow spectrum (2. theta.: 43-46 ℃ C.) of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 3, FIG. 4 contains a dielectric constant versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 3, and FIG. 5 contains a dielectric loss versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 3.
Example 4
This embodiment differs from embodiment 1 only in that: the molar ratios of PbO and CuO added after the pre-firing were 0.79 and 0.21, i.e., 1.5 wt.% (0.79PbO-0.21CuO), and the rest was the same as described in example 1.
FIGS. 1 and 2 contain the piezoelectric constant d of the niobium nickel-lead zirconate titanate piezoelectric ceramic obtained in example 433And electromechanical coupling coefficient kp, room temperature dielectric constant
And a room temperature dielectric loss tan, FIG. 3 contains a full XRD spectrum (2. theta.: 20-80 ℃ C.) and a narrow spectrum (2. theta.: 43-46 ℃ C.) of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 4, FIG. 4 contains a dielectric constant versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 4, and FIG. 5 contains a dielectric loss versus temperature curve at 1kHz of the lead niobium nickel-zirconate titanate piezoelectric ceramic obtained in example 4.
Comparative example 1
The present embodiment is different from embodiment 1 in that:
after pre-sintering, the low-temperature additives PbO and CuO are not added, the pre-sintering powder is directly ground and refined, the mass of the pre-sintering powder is weighed, the pre-sintering powder is added into a nylon ball milling tank, deionized water accounting for 60 percent of the mass of the pre-sintering powder is added, ball milling is carried out, the temperature is kept for 2 hours when the sintering temperature is 1210 ℃, and the rest contents are the same as those in the embodiment 1.
The performance parameters of the obtained piezoelectric ceramics are shown in the following table 1:
FIG. 6 contains the dielectric constant at 1kHz versus temperature curve of the niobium nickel-lead zirconate titanate piezoelectric ceramic prepared in comparative example 1, and FIG. 7 contains the dielectric loss at 1kHz versus temperature curve of the niobium nickel-lead zirconate titanate piezoelectric ceramic prepared in example 1.
Comparative example 2
The present embodiment is different from embodiment 1 in that:
after the pre-sintering, the low-temperature additives PbO and CuO are not added, the pre-sintering powder is directly ground and refined, the mass of the pre-sintering powder is weighed, the pre-sintering powder is added into a nylon ball milling tank, deionized water accounting for 60 percent of the mass of the pre-sintering powder is added, the ball milling is carried out, and the rest contents are the same as those in the embodiment 1.
The performance parameters of the obtained piezoelectric ceramics are shown in the following table 2:
FIG. 3 contains the full spectrum (2. theta.: 20-80 ℃ C.) and the narrow spectrum (2. theta.: 43-46 ℃ C.) of XRD of the niobium nickel-lead zirconate titanate piezoelectric ceramic obtained in comparative example 2.
In examples 1 to 4 of the present invention, low-temperature sintering aids PbO and CuO are added to the pre-sintered powder of niobium nickel-lead zirconate titanate piezoelectric ceramic in different molar ratios to perform low-temperature sintering, in comparative example 1, pure niobium nickel-lead zirconate titanate piezoelectric ceramic is sintered at a higher temperature, in comparative example 2, pure niobium nickel-lead zirconate titanate piezoelectric ceramic is sintered at the same sintering temperature as in examples 1 to 4, as can be seen from fig. 1 and 2, and table 1, after PbO and CuO are added, the piezoelectric and dielectric properties of the ceramic are improved compared with those of pure ceramic at a high temperature, wherein the best properties are obtained at c 0.77, i.e., the molar amount of PbO to PbO-CuO is 77. mol%, and the sintering temperature can be reduced by about 200 ℃. From fig. 3, it can be seen that the full spectrum and narrow spectrum XRD of the niobium nickel-lead zirconate piezoelectric ceramics with different molar ratios of PbO and CuO show that the ceramics prepared in examples 1 to 4 and comparative example 2 are all pure perovskite phases, no second phase is generated, and three and four tetragonal phases coexist. Fig. 4 to 7 are graphs showing the dielectric constant and dielectric loss at 1kHz of the niobium nickel-lead zirconate piezoelectric ceramics prepared in examples 1 to 4 and comparative example 2 as a function of temperature, and it can be found that the curie temperature of all the samples is about 220 ℃, i.e., the curie temperature is not greatly affected by the added PbO-CuO.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
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/ 3Ti2/3)O3-(1-x)Pb(ZryTi1-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)1/3Ti2/3)O3-(1-x)Pb(ZryTi1-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.
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