CN105541413B - A kind of unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics materials of high d33 and preparation method thereof - Google Patents

A kind of unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics materials of high d33 and preparation method thereof Download PDF

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CN105541413B
CN105541413B CN201610077167.7A CN201610077167A CN105541413B CN 105541413 B CN105541413 B CN 105541413B CN 201610077167 A CN201610077167 A CN 201610077167A CN 105541413 B CN105541413 B CN 105541413B
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CN105541413A (en
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杨祖培
康守诚
魏灵灵
晁小练
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Shaanxi Normal University
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Abstract

The invention discloses a kind of high d33Unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material and preparation method thereof, the general formula of the ceramic material is Sr1.85Ca0.15NaNb5O15+ x wt.%M, wherein M=Bi2O3, CuO or Li2CO3, the value of x is 0.1~0.25.The present invention passes through Bi, Cu, Li doping vario-property Sr1.85Ca0.15NaNb5O15, Sr is greatly improved1.85Ca0.15NaNb5O15The d of system media ceramic33.The unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material of the present invention has relatively low dielectric loss, higher maximum dielectric constant, relaxation property is remarkably reinforced, i.e. ceramic material has larger dielectric constant in wide temperature range, in addition the ceramic material has preferable ferroelectric properties, by doping vario-property, reduces coercive field, high temperature air polarizes, and the d of ceramic material is greatly improved33, bring the piezoelectric property of ceramic material into play.The preparation method of ceramic material of the present invention is simple, reproducible, high yield rate.

Description

A kind of high d33Unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material and its preparation Method
Technical field
The invention belongs to electron ceramic material technical fields, and in particular to a kind of high d33Unleaded sodium calcium strontium niobate tungsten bronze type Weight electroceramics material and preparation method thereof.
Background technology
With the development of social progress and the mankind, the micromation of electronic component and environmental protection propose ferroelectric ceramics newly Requirement, that is, require ferro-electric device miniaturization, chip type, filming, integrated, unleaded.It is in addition, more next due to the use of condition It is harsher, it is desirable that ferroelectric ceramics has higher Dielectric, Ferroelectric performance in wide temperature range, and current material system cannot It meets the requirements.Since the 1970s, relaxor ferroelectrics are because its high dielectric property and big electrostriction effect cause The concern of engineering circles, so as to have huge application prospect in terms of multilayer ceramic capacitor, the novel electrostretch device.Tungsten The unleaded niobic acid salt material of bronze structures has flexible and changeable crystal structure advantage and abundant physical performance characteristics, with composition Adjusting and structure change can show peculiar dielectric, ferroelectricity, piezoelectricity, pyroelectricity, nonlinear optical effect and photoelectric effect etc., A kind of important functional material and the critical material of lead-free ferroelectric material research and device research and development are become.Therefore, nothing is explored Lead and the ferroelectric ceramic material new system of high Dielectric, Ferroelectric performance become ferroelectric ceramic material research and device development is urgently to be resolved hurrily One of critical issue.But growth of the unleaded niobic acid salt material of tungsten bronze structure in high-temperature sintering process due to tungsten bronze in itself Habit, the speed of growth in (001) direction are fast, it is easy to generate the rhabdolith of each diversity, so as to deteriorate sintering behavior, Reduce consistency.In view of it is described above, a kind of stabilization, low temperature sintering, high performance high-k weight electricity are provided Ceramic material is the active demand of commercial Application.
Invention content
The technical problems to be solved by the invention be to provide one kind have under relatively low calcined temperature and sintering temperature compared with High Dielectric, Ferroelectric performance, high d33Unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material and the ceramic material system Preparation Method.
It is Sr that scheme, which is the general formula of the ceramic material, used by solution above-mentioned technical problem1.85Ca0.15NaNb5O15+x Wt.%M, wherein x wt.% represent M and account for Sr1.85Ca0.15NaNb5O15Mass percent；The M represents Bi2O3, x takes Be worth is 0.10~0.20；Or M represents Li2CO3, x value be 0.10~0.25；Or M represent the value of CuO, x as 0.10~ 0.15。
Above-mentioned M represents Bi2O3When, the value of x is preferably 0.10~0.15.
Above-mentioned M represents Li2CO3When, the value of x is preferably 0.20.
The high d of the present invention33The preparation method of unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material is by following step group Into：
1st, dispensing
According to general formula Sr1.85Ca0.15NaNb5O15The stoichiometric ratio of+x wt.%M weighs raw material Na2CO3、 SrCO3、 Nb2O5、CaCO3, M and be fitted into nylon tank, be ball-milling medium by abrading-ball, absolute ethyl alcohol of zirconium ball, be sufficiently mixed ball milling 12~18 Hour, separating zirconium ball is 5~10 hours dry at 80~100 DEG C by raw mixture, with mortar grinder, crosses 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace pre-burning 3~5 hours at 1000~1300 DEG C, cooled to room temperature, with grinding Alms bowl is ground, and obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, is ball-milling medium by abrading-ball, absolute ethyl alcohol of zirconium ball, is sufficiently mixed ball milling 10 ~12 hours, separating zirconium ball was 5~10 hours dry at 80~100 DEG C by pre-burning powder, with mortar grinder, crossed 160 mesh sieve.
4th, it is granulated, tabletting
The mass fraction that its quality 40%~50% is added in pre-burning powder after 160 mesh sieve is crossed is 5% polyvinyl alcohol Aqueous solution is granulated, and crosses 80~120 mesh sieve, cylindric blank is pressed into powder compressing machine.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet, be first warming up to 500 DEG C with 380 minutes, keep the temperature 2 hours, then with 3 DEG C/min of heating speed Rate is warming up to 1200~1400 DEG C, is sintered 3~5 hours, with stove cooled to room temperature.
6th, silver ink firing
By the sintered ceramic surface polishing of step 5,0.5~0.6mm thickness is polished to, is wiped over totally, on it with alcohol The silver paste that thickness is 0.01~0.03mm is respectively coated in lower surface, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, natural cooling To room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 180~250 DEG C of air atmospheres, are polarized 10 points under 1kV/mm electric fields Clock, 2kV/mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Nothing Lead sodium calcium strontium niobate tungsten bronze type weight electroceramics material.
In above-mentioned steps 2, the raw mixture preferably crossed step 1 after 80 mesh sieve is placed in alumina crucible, uses agate Stick is compacted, and it is 1.5g/cm to make its compacted density3, capping is placed in resistance furnace pre-burning 4 hours at 1100~1200 DEG C, naturally cold But to room temperature, with mortar grinder, pre-burning powder is obtained.
In above-mentioned steps 5, preferably cylindric blank is placed on zirconium oxide tablet, it is close that zirconium oxide tablet is placed in aluminium oxide It closes in saggar, and pre-burning powder is paved with around zirconium oxide tablet, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, then with 3 DEG C/min heating rate be warming up to 1250~1350 DEG C, be sintered 4 hours, with stove cooled to room temperature.
The unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material of the present invention has relatively low dielectric loss, higher Maximum dielectric constant, relaxation property are remarkably reinforced, i.e., ceramic material has larger dielectric constant in wide temperature range, in addition The ceramic material has preferable ferroelectric properties, by doping vario-property, reduces coercive field, high temperature air polarization increases substantially The d of ceramic material33, bring the piezoelectric property of ceramic material into play.The preparation method of ceramic material of the present invention is simple, repeats The good, high yield rate of property.
Description of the drawings
Fig. 1 is the XRD diagram of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by Examples 1 to 3.
Fig. 2 is the XRD diagram of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by embodiment 4 and 5.
Fig. 3 is the XRD diagram of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by embodiment 6~9.
Fig. 4 is the dielectric temperature spectrum of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by embodiment 1 and dielectric damage Consumption figure.
Fig. 5 is the dielectric temperature spectrum of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by embodiment 4 and dielectric damage Consumption figure.
Fig. 6 is the dielectric temperature spectrum of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by embodiment 8 and dielectric damage Consumption figure.
Fig. 7 is the ferroelectric properties analysis of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by Examples 1 to 3 Figure.
Fig. 8 is the ferroelectric properties analysis of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by embodiment 4 and 5 Figure.
Fig. 9 is the ferroelectric properties analysis of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by embodiment 6~9 Figure.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but the present invention is not limited to these Examples.
Embodiment 1
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15+ 0.10wt.%Bi2O3Stoichiometric ratio, weigh raw material Na2CO3 1.5792g、CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g、Bi2O30.03g is uniformly mixed, raw material is mixed Object is fitted into nylon tank, addition absolute ethyl alcohol and zirconium ball, and the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, use ball milling 401 revs/min of machine is sufficiently mixed ball milling 16 hours, separating zirconium ball, and it is small that raw mixture is placed in 80 DEG C of dryings 12 in drying box When, with mortar grinder 30 minutes, cross 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1200 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1330 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 2
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15+ 0.15wt.%Bi2O3Stoichiometric ratio, weigh raw material Na2CO3 1.5792g、CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g、Bi2O30.045g is uniformly mixed, raw material is mixed Object is fitted into nylon tank, addition absolute ethyl alcohol and zirconium ball, and the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, use ball milling 401 revs/min of machine is sufficiently mixed ball milling 16 hours, separating zirconium ball, and it is small that raw mixture is placed in 80 DEG C of dryings 12 in drying box When, with mortar grinder 30 minutes, cross 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1180 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1300 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 3
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15+ 0.20wt.%Bi2O3Stoichiometric ratio, weigh raw material Na2CO3 1.5792g、CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g、Bi2O30.06g is uniformly mixed, raw material is mixed Object is fitted into nylon tank, addition absolute ethyl alcohol and zirconium ball, and the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, use ball milling 401 revs/min of machine is sufficiently mixed ball milling 16 hours, separating zirconium ball, and it is small that raw mixture is placed in 80 DEG C of dryings 12 in drying box When, with mortar grinder 30 minutes, cross 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1180 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1300 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 4
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15The stoichiometric ratio of+0.10wt.%CuO weighs raw material Na2CO3 1.5792g、 CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g, CuO 0.03g are uniformly mixed, raw mixture are packed into Buddhist nun In imperial tank, absolute ethyl alcohol and zirconium ball are added in, the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, with 401 turns of ball mill/ Minute it is sufficiently mixed ball milling 16 hours, raw mixture is placed in drying box 80 DEG C of dryings 12 hours, uses mortar by separating zirconium ball 80 mesh sieve is crossed in grinding 30 minutes.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1200 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1330 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 5
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15The stoichiometric ratio of+0.15wt.%CuO weighs raw material Na2CO3 1.5792g、 CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g, CuO 0.045g are uniformly mixed, raw mixture are packed into Buddhist nun In imperial tank, absolute ethyl alcohol and zirconium ball are added in, the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, with 401 turns of ball mill/ Minute it is sufficiently mixed ball milling 16 hours, raw mixture is placed in drying box 80 DEG C of dryings 12 hours, uses mortar by separating zirconium ball 80 mesh sieve is crossed in grinding 30 minutes.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1200 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1300 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 6
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15+ 0.10wt.%Li2CO3Stoichiometric ratio, weigh raw material Na2CO3 1.5792g、CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g、Li2CO30.03g is uniformly mixed, raw material is mixed Object is fitted into nylon tank, addition absolute ethyl alcohol and zirconium ball, and the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, use ball milling 401 revs/min of machine is sufficiently mixed ball milling 16 hours, separating zirconium ball, and it is small that raw mixture is placed in 80 DEG C of dryings 12 in drying box When, with mortar grinder 30 minutes, cross 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1200 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1330 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 7
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15+ 0.15wt.%Li2CO3Stoichiometric ratio, weigh raw material Na2CO3 1.5792g、CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g、Li2CO30.045g is uniformly mixed, raw material is mixed It closes object to be fitted into nylon tank, addition absolute ethyl alcohol and zirconium ball, the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, use ball 401 revs/min of grinding machine is sufficiently mixed ball milling 16 hours, separating zirconium ball, and raw mixture is placed in 80 DEG C of dryings 12 in drying box Hour, with mortar grinder 30 minutes, cross 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1180 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1300 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 8
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15+ 0.20wt.%Li2CO3Stoichiometric ratio, weigh raw material Na2CO3 1.5792g、CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g、Li2CO30.06g is uniformly mixed, raw material is mixed Object is fitted into nylon tank, addition absolute ethyl alcohol and zirconium ball, and the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, use ball milling 401 revs/min of machine is sufficiently mixed ball milling 16 hours, separating zirconium ball, and it is small that raw mixture is placed in 80 DEG C of dryings 12 in drying box When, with mortar grinder 30 minutes, cross 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1180 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1300 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Embodiment 9
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15+ 0.25wt.%Li2CO3Stoichiometric ratio, weigh raw material Na2CO3 1.5792g、CaCO30.4510g、Nb2O519.7652g、SrCO38.2046g、Li2CO30.075g is uniformly mixed, raw material is mixed It closes object to be fitted into nylon tank, addition absolute ethyl alcohol and zirconium ball, the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, use ball 401 revs/min of grinding machine is sufficiently mixed ball milling 16 hours, separating zirconium ball, and raw mixture is placed in 80 DEG C of dryings 12 in drying box Hour, with mortar grinder 30 minutes, cross 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1180 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1280 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/ Mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded SrNb2 O6 Calcium sodium tungsten bronze type weight electroceramics material.
Comparative example 1
1st, dispensing
According to Sr1.85Ca0.15NaNb5O15Stoichiometric ratio, weigh raw material Na2CO31.5792g、CaCO3 0.4510g、 Nb2O519.7652g、SrCO38.2046g is uniformly mixed, raw mixture is fitted into nylon tank, adds in absolute ethyl alcohol and zirconium The mass ratio of ball, absolute ethyl alcohol and raw mixture is 1:1.2, it is sufficiently mixed ball milling 16 hours for 401 revs/min with ball mill, Raw mixture is placed in drying box 80 DEG C of dryings 12 hours by separating zirconium ball, with mortar grinder 30 minutes, crosses 80 mesh sieve.
2nd, pre-burning
Raw mixture step 1 crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace 1230 DEG C of pre-burnings 4 hours, and cooled to room temperature is divided with mortar grinder 10 Clock obtains pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, absolute ethyl alcohol and zirconium ball is added in, ball is sufficiently mixed for 401 revs/min with ball mill Pre-burning powder is placed in drying box 80 DEG C of drying 10 hours by mill 12 hours, separating zirconium ball, with mortar grinder 10 minutes, mistake 160 Mesh sieves.
4th, it is granulated, tabletting
It is crossed to 10g and the polyvinyl alcohol water solution that 5g mass fractions are 5% is added in the pre-burning powder after 160 mesh sieve, be granulated, mistake 120 mesh sieve, and spherical powder is made, spherical powder is put into the stainless steel mould of a diameter of 15mm, is existed with powder compressing machine The cylindric blank that thickness is 1.5mm is compressed under the pressure of 100MPa.
5th, it is sintered
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in oxygen Change and be paved with pre-burning powder around zirconium tablet to compensate the volatilization of component, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, excluded Machine object, then 1350 DEG C are warming up to 3 DEG C/min of heating rate, it is sintered 4 hours, with stove cooled to room temperature.
6th, silver ink firing
The sand paper that the sintered ceramics of step 5 are chosen to 320 mesh of one of sample surfaces is polished, then with 800 mesh Sand paper polishing, be finally wiped over totally with alcohol, on it following table to 0.5mm thickness with the sand paper of 1600 mesh and diamond polishing Face coating thickness is the silver paste of 0.02mm, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, cooled to room temperature.
7th, it polarizes
Ceramics after step 6 silver ink firing are placed in room temperature silicone oil, are polarized 10 minutes under 1kV/mm electric fields, 2kV/mm electricity Field polarization 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain sodium calcium strontium niobate tungsten bronze type Weight electroceramics material.
Comparative example 2
In the step 7 of comparative example 1, the ceramics after step 6 silver ink firing are placed in 190 DEG C of air atmospheres, in 1kV/mm electricity It polarizes 10 minutes off field, 2kV/mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 divide Clock, other steps are identical with comparative example 1, obtain sodium calcium strontium niobate tungsten bronze type weight electroceramics material.
The niobic acid that inventor prepares Examples 1 to 9 and comparative example 1 and 2 using D/max-2200X types x ray diffractometer x Strontium calcium sodium tungsten bronze type weight electroceramics material carries out structural characterization, using quasi-static d33Tester is to Examples 1 to 9 and right The d of sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by ratio 1 and 233, and pass through following formula and calculate permittivity εr：
εr=4Ct/ (π ε0d)
In formula, C is capacitance, and t is the thickness of potsherd, ε0For permittivity of vacuum (8.85 × 10-12F/m), d is ceramics The diameter of piece.As a result the result is shown in Figure 1~9 and table 1.
The Dielectric, Ferroelectric performance of the weight electroceramics material of 1 Examples 1 to 9 of table and comparative example 1 and 2
Weight electroceramics material εm Tc(℃) d33
Comparative example 1 1449 308 32
Comparative example 2 1449 308 76
Embodiment 1 1317 297 136
Embodiment 2 1261 295.7 119
Embodiment 3 1193 291 102
Embodiment 4 1579 304 149
Embodiment 5 1490 300 138
Embodiment 6 1568 308 91
Embodiment 7 1690 304 101
Embodiment 8 1701 304 121
Embodiment 9 1718 300 97
By Fig. 1~3 as it can be seen that sodium calcium strontium niobate tungsten bronze type weight electroceramics material prepared by Examples 1 to 9 is respectively formed Pure quadratic tungsten bronze structure (TTB) phase, does not find other miscellaneous peaks.By Fig. 4~9 and table 1 as it can be seen that niobium prepared by Examples 1 to 9 The dielectric constant of sour strontium calcium sodium tungsten bronze type weight electroceramics material is at the iron bullet ferroelectric phase transition and Curie temperature of near room temperature Higher, dielectric loss is relatively low, and can obtain the ferroelectric hysteresis loop of saturation, and ferroelectric properties is excellent, and niobium prepared by comparative example 1 and 2 The ferroelectric properties of sour strontium calcium sodium tungsten bronze type weight electroceramics material is poor, d33It is relatively low, absolutely prove appropriate Bi, Cu, Li Introducing optimize the electric property of sodium calcium strontium niobate tungsten bronze type weight electroceramics；Comparative example 1 compares with 2, illustrates this hair Bright high-temperature poling condition gives full play of the piezoelectric property of sodium calcium strontium niobate tungsten bronze type weight electroceramics, greatly improves Its d33。

Claims (3)

1. a kind of high d33The preparation method of unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material, the general formula of the ceramic material For Sr1.85Ca0.15NaNb5O15+ x wt.% M, wherein x wt.% represent M and account for Sr1.85Ca0.15NaNb5O15Mass percent；Institute The M stated represents CuO, and the value of x is 0.10~0.15；It is characterized in that the preparation method of the ceramic material is by following step group Into：
（1）Dispensing
According to general formula Sr1.85Ca0.15NaNb5O15The stoichiometric ratio of+x wt.% M, weighs raw material Na2CO3、SrCO3、Nb2O5、 CaCO3, M and be fitted into nylon tank, be ball-milling medium by abrading-ball, absolute ethyl alcohol of zirconium ball, be sufficiently mixed ball milling 12~18 hours, Separating zirconium ball, raw mixture is 5~10 hours dry at 80~100 DEG C, with mortar grinder, cross 80 mesh sieve；
（2）Pre-burning
By step（1）The raw mixture crossed after 80 mesh sieve is placed in alumina crucible, is compacted with agate stick, is made its compacting close It spends for 1.5g/cm3, capping is placed in resistance furnace pre-burning 3~5 hours at 1000~1300 DEG C, cooled to room temperature, with grinding Alms bowl is ground, and obtains pre-burning powder；
（3）Secondary ball milling
Pre-burning powder is fitted into nylon tank, is ball-milling medium by abrading-ball, absolute ethyl alcohol of zirconium ball, it is small to be sufficiently mixed ball milling 10~12 When, separating zirconium ball is 5~10 hours dry at 80~100 DEG C by pre-burning powder, with mortar grinder, crosses 160 mesh sieve；
（4）It is granulated, tabletting
The mass fraction that its quality 40%~50% is added in pre-burning powder after 160 mesh sieve is crossed is 5% polyvinyl alcohol water solution, It is granulated, crosses 80~120 mesh sieve, cylindric blank is pressed into powder compressing machine；
（5）Sintering
Cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in the closed saggar of aluminium oxide, and in zirconium oxide Pre-burning powder is paved with around tablet, was first warming up to 500 DEG C with 380 minutes, keeps the temperature 2 hours, then with 3 DEG C/min of heating rate liter Temperature is sintered 3~5 hours, to 1200~1400 DEG C with stove cooled to room temperature；
（6）Silver ink firing
By step（5）The polishing of sintered ceramic surface is polished to 0.5~0.6 mm thickness, is wiped over totally with alcohol, on it under The silver paste that thickness is 0.01~0.03 mm is respectively coated in surface, is placed in resistance furnace and keeps the temperature 30 minutes for 840 DEG C, naturally cools to Room temperature；
（7）Polarization
By step（6）Ceramics after silver ink firing are placed in 180~250 DEG C of air atmospheres, are polarized 10 minutes under 1kV/mm electric fields, 2kV/mm electric field polarizations 20 minutes, 3kV/mm electric field polarizations 30 minutes, 4kV/mm electric field polarizations 40 minutes obtain high d33Unleaded niobium Sour strontium calcium sodium tungsten bronze type weight electroceramics material.
2. high d according to claim 133The preparation method of unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material, It is characterized in that：The step（2）In, by step（1）The raw mixture crossed after 80 mesh sieve is placed in alumina crucible, uses agate Nao sticks are compacted, and it is 1.5g/cm to make its compacted density3, it is capped, is placed in resistance furnace pre-burning 4 hours at 1100~1200 DEG C, from It is so cooled to room temperature, with mortar grinder, obtains pre-burning powder.
3. high d according to claim 133The preparation method of unleaded sodium calcium strontium niobate tungsten bronze type weight electroceramics material, It is characterized in that：The step（5）In, cylindric blank is placed on zirconium oxide tablet, zirconium oxide tablet is placed in aluminium oxide In closed saggar, and pre-burning powder is paved with around zirconium oxide tablet, first rose to 500 DEG C with 380 minutes, keep the temperature 2 hours, then with 3 DEG C/min heating rate be warming up to 1250~1350 DEG C, be sintered 4 hours, with stove cooled to room temperature.
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CN107188564B (en) * 2017-07-14 2019-12-03 陕西师范大学 A kind of Eu of high dielectric property3+Adulterate luminous ferroelectric ceramic material of sodium calcium strontium niobate and preparation method thereof
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