CN109665837B - Novel ferroelectric ceramic material for explosive electrical energy conversion and preparation method thereof - Google Patents

Novel ferroelectric ceramic material for explosive electrical energy conversion and preparation method thereof Download PDF

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CN109665837B
CN109665837B CN201710961790.3A CN201710961790A CN109665837B CN 109665837 B CN109665837 B CN 109665837B CN 201710961790 A CN201710961790 A CN 201710961790A CN 109665837 B CN109665837 B CN 109665837B
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王根水
苏日古
聂恒昌
董显林
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to aThe novel ferroelectric ceramic material for explosive electric energy conversion and the preparation method thereof, the chemical components of the ferroelectric ceramic material conform to the chemical general formula (1-x) PbZrO3‑xBa(Mg1/3Nb2/3)O3Wherein 0.01. ltoreq. x.ltoreq.0.05, preferably 0.025. ltoreq. x.ltoreq.0.035. The ferroelectric ceramic material for the explosive electric energy conversion has the characteristics of high residual polarization intensity, phase change depolarization of a polarization sample under lower isostatic pressure and the like, and can meet the requirements of manufacturing an explosive electric energy conversion element.

Description

Novel ferroelectric ceramic material for explosive electrical energy conversion and preparation method thereof
Technical Field
The invention relates to a lead zirconate-based ceramic material and a preparation method thereof, in particular to a novel ferroelectric ceramic material for electric explosion transduction and a preparation method thereof, belonging to the technical field of ferroelectric ceramic materials.
Background
The working principle of the ferroelectric pulse power supply is as follows: the ferroelectric material at the phase boundary has a certain remanent polarization P after polarizationrUnder the action of the shock wave, the polarized ferroelectric material can be rapidly depolarized within a few microseconds to release bound charges on the surface, so that strong current pulse (in the case of low-impedance load) or voltage pulse (in the case of high-impedance load) energy is output. The device has important application in pulse power supply with high energy storage density.
At present, PZT95/5 ferroelectric ceramic (Pb (Zr) is the most widely used in research and application using the ferroelectric ceramic as a pulse power source0.95Ti0.05)O3(ii) a The ratio of zirconium to titanium is 95: 5 lead zirconate titanate ferroelectric ceramic). The PZT95/5 ferroelectric ceramic material is near the ferroelectric-antiferroelectric phase boundary, is antiferroelectric phase at room temperature, changes into metastable ferroelectric phase after polarization, and instantly and completely depolarizes under the action of impact stress to release surface bound charges to change into antiferroelectric phase. The released energy can reach megawatt level, and is widely applied to the aspect of explosive power conversion.
But PZT95/5 ferroelectric material is at 40-Has a high-low temperature phase change F within the temperature range of 50 DEG CRLT-FRHTThe stability of the material is reduced, and the application in certain environments is limited. Therefore, a material which has no high-low temperature phase transition and high residual polarization intensity after polarization of the material and is depolarized by stress-induced phase transition can be prepared.
Disclosure of Invention
In view of the above problems of the prior art, an object of the present invention is to provide a ceramic material having high remanent polarization after polarization, stress-induced phase transition depolarization, and no high-low temperature phase transition as described above, which can be applied to electrical explosion transduction, and a method for preparing the same.
In one aspect, the present invention provides a ferroelectric ceramic material for use in detonation electro-transduction, having a chemical composition corresponding to the general chemical formula (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3Wherein x is more than or equal to 0.01 and less than or equal to 0.05.
The ferroelectric ceramic material for the explosive electric energy conversion has the characteristics of high residual polarization intensity, phase change depolarization of a polarization sample under lower isostatic pressure and the like, and can meet the requirements of manufacturing an explosive electric energy conversion element; compared with PZT95/5 ceramic widely used in explosive electric energy conversion at present, the high and low temperature ferroelectric phase transition (F) is avoidedRLT-FRHT) The characteristic of energy storage density reduction of the PZT95/5 explosion electricity transducing material under high temperature can be solved.
Preferably, x is more than or equal to 0.025 and less than or equal to 0.035.
Preferably, the residual polarization strength of the ferroelectric ceramic material can reach 30.8 μ C/cm at an electric field of 3kV/mm2The above.
In another aspect, the present invention provides a method for preparing the ferroelectric ceramic material, including:
solid phase method for synthesizing MgNb2O6Powder;
according to the chemical formula (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3Weighing Pb source, Zr source, Ba source and the MgNb in stoichiometric ratio2O6Uniformly mixing the powder to obtain mixed powder;
mixing the mixed powderBriquetting, synthesizing (1-x) PbZrO in lead-rich atmosphere3-xBa(Mg1/3Nb2/3)O3Powder;
subjecting the (1-x) PbZrO to3-xBa(Mg1/3Nb2/3)O3Pulverizing the powder, sieving, grinding, oven drying, adding binder, granulating, aging, sieving, molding, and removing plastic to obtain blank;
and sintering the blank in a lead-rich atmosphere to obtain the ferroelectric ceramic material.
The invention adopts a precursor synthesis method, and utilizes the prepared niobium-iron ore precursor to be mixed with a Pb source, a Zr source and a Ba source to synthesize (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3Preparing the powder into a blank, and sintering to obtain (1-x) PbZrO3-xBa(Mg1/ 3Nb2/3)O3Ferroelectric ceramic materials. The precursor synthesis method has the advantages of easy obtaining of pure perovskite structure ceramics, simple process, low cost, no need of special equipment and the like. By regulating Ba (Mg)1/3Nb2/3)O3The content of the components can ensure that the ferroelectric ceramic material has high residual polarization intensity after polarization (30 mu C/cm at 3 kV/mm)2) The ferroelectric ceramic material can also be subjected to phase change depolarization under lower isostatic pressure (200-238 MPa), and can be applied to the explosion electric transduction; the ferroelectric ceramic material of the invention has no high and low temperature phase transition F by adjusting the x component through composition designRLT-FRHTThereby being expected to become more ideal explosion electricity transduction materials in the future. The preparation method has the advantages of simple process, no need of special equipment, low cost and the like, is suitable for large-scale production, and can meet the industrial requirements.
Preferably, MgNb is synthesized by solid phase method2O6The powder comprises: with MgCO3、Nb2O5The powder is taken as a raw material and MgNb is adopted according to a chemical formula2O6Weighing stoichiometric MgCO3、Nb2O5Uniformly mixing the powder, drying, briquetting, and keeping the temperature of 1000-1100 ℃ for 1-5 hours in the atmosphere to obtain the MgNb powder2O6A niobite precursor ofCrushing and sieving the precursor to obtain the MgNb2O6And (3) powder.
In the present invention, the MgCO may be used3、Nb2O5Uniformly mixing the powder, drying and adding the MgCO by mass before briquetting3、Nb2O55-15% of water based on the total mass of the powder.
Preferably, the Pb source is Pb3O4The Zr source is ZrO2The Ba source is BaCO3。
Preferably, (1-x) PbZrO is synthesized3-xBa(Mg1/3Nb2/3)O3The temperature of the powder is 800-900 ℃, and the heat preservation time is 1-5 hours.
Preferably, the binder is polyvinyl alcohol or polyvinyl butyral, and the usage amount of the binder is (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O36-7% of the powder mass.
Preferably, the aging time is 22 to 26 hours.
Preferably, the temperature of the plastic discharging is 800-850 ℃, and the heat preservation time is 1-4 hours.
Preferably, the sintering temperature is 1300-1350 ℃, and the heat preservation time is 1-6 hours.
Drawings
FIG. 1 is an electrical hysteresis curve diagram of the novel ferroelectric ceramic material for use in electrical explosion transduction prepared in example 1 under different electric field conditions;
FIG. 2 is a diagram showing the depolarisation process under isostatic pressure of the novel ferroelectric ceramic material for explosive electric energy transducer prepared in example 1;
FIG. 3 is the dielectric thermogram of the ferroelectric ceramic material for polarized detonation-electric transducer prepared in example 1 at different frequencies.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are intended to illustrate and not to limit the present invention.
The invention relates to a novel ferroelectric ceramic for explosive electrical energy conversionThe chemical formula of the composition of the material is (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3Wherein x is 0.01-0.05, preferably 0.025-0.035. The ceramic material of the invention adopts a precursor synthesis method, and utilizes the prepared niobite precursor to be mixed with a Pb source, a Zr source and a Ba source to synthesize (1-x) PbZrO3-xBa(Mg1/ 3Nb2/3)O3Preparing the powder into a blank, and sintering to obtain the powder. The preparation method has the advantages of simple process, no need of special equipment, low cost and the like, is suitable for large-scale production, and can meet the requirement of industrial production.
The preparation of (1-x) PbZrO of the present invention is specifically described below3-xBa(Mg1/3Nb2/3)O3A method of ferroelectric ceramic material.
First, a niobite precursor is prepared, the chemical composition of which is MgNb2O6. In the invention, MgNb is synthesized by a solid phase method2O6A precursor. In particular, MgCO is used3、Nb2O5The powder is taken as a raw material and MgNb is adopted according to a chemical formula2O6Weighing stoichiometric MgCO3、Nb2O5Uniformly mixing the powder, drying, briquetting, and keeping the temperature of 1000-1100 ℃ for 1-5 hours (for example, 2 hours) in the atmosphere to obtain MgNb2O6A precursor. MgCO3、Nb2O5The mixing method of the powder can adopt a wet ball milling process and the like. In one example, MgCO3、Nb2O5The mixing of the powder includes, for example: the mass ratio of the ball grinding material to the ball grinding medium to the deionized water is 1: (1-1.5): (0.6-1.0), the ball milling time is 12-24 h, and the ball milling medium can be steel balls, zirconium balls or agate balls and the like.
In the present invention, the MgCO may be used3、Nb2O5After the powder is uniformly mixed and dried, water with the total weight of 5-15% (for example, 10%) of the powder is added before briquetting, so that the powder can react more completely. MgCO3、Nb2O5The briquetting of the mixed powder can be carried out by a press vulcanizer method comprising charging the powder into a mold and placing the powder on both sides of a press vulcanizerAnd (3) adding 4-8 MPa of pressure, maintaining the pressure for 10-30 seconds, releasing the pressure, and performing compression molding. MgNb prepared by the solid phase method as above2O6The precursor can more easily obtain a pure perovskite structure.
Prepared MgNb2O6The precursor is crushed and sieved (for example, 30-mesh sieve), and MgNb is obtained2O6And (3) powder.
Then, PbZrO was formed according to the general chemical formula (1-x)3-xBa(Mg1/3Nb2/3)O3Weighing Pb source, Zr source, Ba source and MgNb source in stoichiometric ratio2O6And uniformly mixing the powder to obtain mixed powder. In the present invention, Pb is used as the Pb source3O4(ii) a The Zr source adopts ZrO2(ii) a The Ba source adopts BaCO3. The mixing method of the above powder may adopt a wet ball milling process, and the like, and for example, includes: the mass ratio of the ball grinding material to the ball grinding medium to the deionized water is 1: (1-1.5): (0.6-1.0), the ball milling time is 12-24 h, and the ball milling medium can be steel balls, zirconium balls or agate balls and the like.
Then, the mixed powder was briquetted to synthesize (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3And (3) powder. Specifically, the mixed powder is dried and pressed into a large block, and the large block is synthesized in a lead-rich atmosphere at the synthesis temperature of 800-900 ℃ for 1-5 hours (for example, 4 hours) to obtain the PbZrO with the composition of (1-x)3-xBa(Mg1/3Nb2/3)O3The powder of (4). The synthesis under the lead-rich atmosphere has the advantage of reducing the volatilization of lead. In addition, water accounting for 10 percent of the total powder mass can be added after the mixed powder is dried and before briquetting.
Then, the obtained (1-x) PbZrO was subjected to heat treatment3-xBa(Mg1/3Nb2/3)O3And (4) crushing, sieving and grinding the powder. The grinding may be performed by, for example, a wet ball milling process, and the like, and includes, for example: the mass ratio of the ball grinding material to the ball grinding medium to the deionized water is 1: (1.5-2.0): (0.5-1.0), the ball milling time is 12-24 h, and the ball milling medium can be steel balls, zirconium balls or agate balls. Further, the sieving may be, for example, 30 mesh sieving before wet ball milling.
Then, willMilled (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3And adding a binder into the powder for granulation, aging, sieving, and performing compression molding to obtain a biscuit. In the invention, the binder can adopt polyvinyl alcohol (PVA), polyvinyl butyral (PVB) and the like, and the usage amount of the binder is 6-7% of the mass of the powder. The aging time can be 22-26 h. When the aging time is 22-26 h, the ceramic has the advantage of being not easy to delaminate. In addition, 30 mesh screens may be used prior to molding.
In the present invention, the obtained biscuit is subjected to a temperature to remove organic substances (plastic removal) from the biscuit. In the invention, the temperature for plastic removal can be 800-850 ℃, and the heat preservation time is 1-4 hours (for example, 2 hours). Through plastic removal, organic matters can be removed in advance, and defects such as holes and microcracks generated in materials are avoided.
Then, sintering the green body after plastic removal in a lead-rich atmosphere to obtain (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3Ferroelectric ceramic materials. In the invention, the sintering process conditions are as follows: the sintering temperature is 1300-1350 ℃, and the temperature is kept for 1-6 hours (for example, 4 hours). The temperature rise rate of the sintering can be 1-3 ℃/min (for example, 2 ℃/min).
The novel ferroelectric ceramic material for the explosion electric energy conversion has the characteristics of high residual polarization intensity, phase change depolarization of a polarization sample under lower isostatic pressure and the like, and can meet the requirements for manufacturing an explosion electric energy conversion element; compared with PZT95/5 ceramic widely used in explosive electric energy conversion at present, the high and low temperature ferroelectric phase transition (F) is avoidedRLT-FRHT) The characteristic of energy storage density reduction of the PZT95/5 explosion electricity transduction material at high temperature is solved.
In addition, in the invention, after the sintered sample is cut off, the grain size, the micropore and other microstructures of the sample can be observed by using a scanning electron microscope; processing the sintered ceramic material into a required size, ultrasonically cleaning, screen-printing silver paste, drying, and preserving heat at 750-800 ℃ for 10-30 minutes to obtain (1-x) PbZrO evaluated in electrical property3-xBa(Mg1/3Nb2/3)O3。
The invention has the advantages that:
novel exploder of the inventionThe ferroelectric ceramic material for the electric transduction not only has high residual polarization intensity (30 mu C/cm at 3 kV/mm)2) The phase change depolarization under lower isostatic pressure (200-238 MPa), can be applied to the explosion electric transduction, and has no high-low temperature phase change FRLT-FRHTThereby being expected to become a more ideal material for the explosion electricity transduction in the future;
the preparation method has the advantages of simple process, no need of special equipment, low cost and the like, is suitable for large-scale production, and can meet the industrial requirements.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Firstly according to the chemical formula MgNb2O6Taking MgCO in stoichiometric ratio3And Nb2O5Mixing the two kinds of powder evenly by a wet ball milling process; the mass ratio of the ball grinding material to the ball grinding medium to the deionized water is 1: 1.5: 0.86, the ball milling time is 24 hours, and the ball milling medium is iron balls;
drying, adding deionized water accounting for 10% of the total powder mass, briquetting, and synthesizing in an atmosphere at 1100 ℃ for 2h to obtain MgNb2O6The niobite precursor of (a); pulverizing, and sieving with 30 mesh sieve;
according to the chemical formula 0.97PbZrO3-0.03Ba(Mg1/3Nb2/3)O3Weighing Pb in stoichiometric ratio3O4、ZrO2、BaCO3And the MgNb prepared2O6Powder, and all the powder is uniformly mixed by a wet ball milling process; the mass ratio of the ball grinding material to the ball grinding medium to the deionized water is 1: 1.5: 0.86, the ball milling time is 24 hours, and the ball milling medium is iron balls;
drying, adding deionized water accounting for 10% of the total powder mass, briquetting, synthesizing in a lead-rich atmosphere at 850 ℃, and keeping the temperature for 4h to obtain the product with the composition of 0.97PbZrO3-0.03Ba(Mg1/3Nb2/3)O3The powder of (4); crushing, sieving with a 30-mesh sieve, and uniformly mixing the powder by using a wet ball milling process; the mass ratio of the ball grinding material to the ball grinding medium to the deionized water is 1: 1.5: 0.6, the ball milling time is 24 hours, and the ball milling medium is iron balls;
drying, adding a polyvinyl alcohol (PVA) binder with the powder mass of 6-7%, granulating, aging for 24 hours, sieving with a 30-mesh sieve, forming, and performing plastic discharge at 850 ℃ to obtain the 0.97PbZrO3-0.03Ba(Mg1/3Nb2/3)O3A green body; sintering the blank in a lead-rich atmosphere, wherein the sintering process conditions are as follows: heating to 1300-1350 ℃ at the heating rate of 2 ℃/min, preserving heat for 4h, and cooling to room temperature along with the furnace;
processing the sintered sample into a required size, ultrasonically cleaning, screen-printing silver paste, drying, keeping the temperature at 750-800 ℃ for 10-30 minutes, and measuring the electric hysteresis loop and the dielectric temperature spectrum.
Fig. 1 is an electrical hysteresis curve diagram of the novel ferroelectric ceramic material for explosive electrical transduction prepared in this embodiment under different electric field conditions, as can be seen from the figure: the ferroelectric hysteresis loop is saturated when the electric field is 3kV/mm, and the remanent polarization is 30.8 mu C/cm2And the coercive field is 1.0 kV/mm.
FIG. 2 is a graph showing the depolarization process under isostatic pressure of the novel ferroelectric ceramic material for explosive electrical energy conversion prepared in this example, wherein the depolarization process starts under a lower isostatic pressure (200MPa), and the depolarization intensity is 27.9 μ C/cm at 238MPa2The depolarization rate can reach 90.58%.
Fig. 3 is a dielectric thermogram of the polarized ferroelectric ceramic material for use in the electro-explosive transduction prepared in this embodiment at different frequencies, as shown in fig. 3: the dielectric constant of the material at room temperature is 342, the highest dielectric constant can reach 15833, the Curie temperature is 194 ℃, and the material does not change along with the frequency; there is no other phase change in the measured temperature range, i.e. there is no other phase changeAbsence of FRLT-FRHTAnd (5) phase transition.
The results of the above tests are shown in Table 1.
Example 2
The present embodiment is different from embodiment 2 in that: according to the chemical formula 0.975PbZrO3-0.025Ba(Mg1/ 3Nb2/3)O3Weighing Pb in stoichiometric ratio3O4、ZrO2、BaCO3And the MgNb prepared2O6And (3) powder.
The remainder of this example was the same as that described in example 1, and the results of the performance testing of the prepared samples are shown in Table 1.
Example 3
The present embodiment is different from embodiment 2 in that: PbZrO according to the chemical formula 0.9653-0.035Ba(Mg1/ 3Nb2/3)O3Weighing Pb in stoichiometric ratio3O4、ZrO2、BaCO3And the MgNb prepared2O6And (3) powder.
The remainder of this example was the same as that described in example 1, and the results of the performance testing of the prepared samples are shown in Table 1.
Table 1 results of performance testing of samples prepared in examples 1 to 3:
Figure BDA0001435403390000061
as can be seen from table 1: the ferroelectric ceramic material ((1-x) PbZrO)3-xBa(Mg1/3Nb2/3)O3) Certain properties of with Ba (Mg)1/3Nb2/3)O3The content is changed regularly; as x increases, the room temperature dielectric constant gradually increases and the Curie temperature decreases, and the remanent polarization and the highest dielectric constant before increase and after decrease. The remanent polarization obtained when x is 0.03 is maximum (30.8 μ C/cm)2) And depolarization is started under lower isostatic pressure (200MPa) to release charges, and the depolarization rate can reach 90.58% at 238 MPa. And is compatible with conventional explosivesThe electro-transducing material PZT95/5 is compared without FRLT-FRHTAnd (5) phase transition. Can meet the application requirement of the explosion electricity transduction material.

Claims (9)

1. The ferroelectric ceramic material for explosive electric energy conversion is characterized in that the chemical components conform to the chemical general formula (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3Wherein x is more than or equal to 0.03 and less than or equal to 0.035, and the residual polarization intensity of the ferroelectric ceramic material can reach 30.8 mu C/cm when the electric field is 3kV/mm2Said ferroelectric ceramic material has no high-low temperature ferroelectric phase transition FRLT-FRHT。
2. A method of preparing a ferroelectric ceramic material according to claim 1, comprising:
solid phase method for synthesizing MgNb2O6Powder;
according to the chemical formula (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O3Weighing Pb source, Zr source, Ba source and the MgNb in stoichiometric ratio2O6Uniformly mixing the powder to obtain mixed powder;
briquetting the mixed powder, and synthesizing (1-x) PbZrO in lead-rich atmosphere3-xBa(Mg1/3Nb2/3)O3Powder;
subjecting the (1-x) PbZrO to3-xBa(Mg1/3Nb2/3)O3Pulverizing the powder, sieving, grinding, oven drying, adding binder, granulating, aging, sieving, molding, and removing plastic to obtain blank;
and sintering the blank in a lead-rich atmosphere to obtain the ferroelectric ceramic material.
3. The method according to claim 2, wherein the MgNb is synthesized by a solid phase method2O6The powder comprises: with MgCO3、Nb2O5The powder is taken as a raw material and MgNb is adopted according to a chemical formula2O6Weighing stoichiometric MgCO3、Nb2O5Mixing the powder evenlyDrying, briquetting, and keeping the temperature of 1000-1100 ℃ for 1-5 hours in the atmosphere to obtain MgNb2O6Crushing and sieving the precursor to obtain the MgNb2O6And (3) powder.
4. The production method according to claim 2, wherein the Pb source is Pb3O4The Zr source is ZrO2The Ba source is BaCO3。
5. The production method according to claim 2, wherein (1-x) PbZrO is synthesized3-xBa(Mg1/3Nb2/3)O3The temperature of the powder is 800-900 ℃, and the heat preservation time is 1-5 hours.
6. The method according to claim 2, wherein the binder is polyvinyl alcohol or polyvinyl butyral and is used in an amount of the (1-x) PbZrO3-xBa(Mg1/3Nb2/3)O36-7% of the powder mass.
7. The method according to claim 2, wherein the aging time is 22 to 26 hours.
8. The preparation method according to claim 2, wherein the temperature of the plastic discharge is 800-850 ℃, and the holding time is 1-4 hours.
9. The method according to any one of claims 2 to 8, wherein the sintering temperature is 1300 to 1350 ℃ and the holding time is 1 to 6 hours.
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