CN106588011A - Potassium sodium niobate-based leadless transparent ferroelectric ceramic with high remanent polarization and high Curie temperature, and production method thereof - Google Patents

Potassium sodium niobate-based leadless transparent ferroelectric ceramic with high remanent polarization and high Curie temperature, and production method thereof Download PDF

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CN106588011A
CN106588011A CN201611266530.6A CN201611266530A CN106588011A CN 106588011 A CN106588011 A CN 106588011A CN 201611266530 A CN201611266530 A CN 201611266530A CN 106588011 A CN106588011 A CN 106588011A
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curie temperature
remanent polarization
ceramics
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CN106588011B (en
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杨祖培
赵旭梅
晁小练
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Shaanxi Normal University
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Abstract

The invention discloses a potassium sodium niobate-based leadless transparent ferroelectric ceramic with high remanent polarization and high Curie temperature, and a production method thereof. The general formula of the ceramic is (1-x)(K0.5Na0.5)NbO3-xCa(Mg1/3Ta2/3)O3, x is 0.02-0.06, and the above ceramic material is produced through a high temperature solid phase technology. The production method has the advantages of simplicity, good repeatability and high yield, the obtained ceramic material has excellent electric performances and certain light transmittance, the transmittance in the near infrared region is 42-64%, the maximum dielectric constant is 2563-4190, the curie temperature is 203-361 DEG C, the dielectric loss is 0.035-0.04, the maximum polarization intensity is 22.2-32.6 [mu]C/cm<2>, the remanent polarization intensity is 6.6-21.6 [mu]C/cm<2>, and the dielectric constant is 28-99 pC/N.

Description

The potassium niobate sodium base leadless transparent ferroelectric ceramics of high remanent polarization and Curie temperature And preparation method thereof
Technical field
The invention belongs to technical field of ceramic material, and in particular to the niobic acid of a kind of high remanent polarization and Curie temperature Potassium sodio Lead-free transparent ferroelectric ceramics, and the ceramic preparation method.
Background technology
Today's society, piezoelectricity, ferroelectric material are used widely on photoelectric device as the important functional material of a class. The advantages of ceramic piezoelectric material is with its stable performance, low production cost becomes the important component part of piezoelectric.Phase Than in conventional piezoelectric, ferroelectric ceramics, transparent relaxation ferroelectric ceramic has more excellent ferroelectricity, optical property and significant electric light Effect, is expected to become indispensable following optical computer technology and the critical material in modern advanced.
The transparent ferroelectric ceramics of application is mainly lead zirconate titanate (PZT) base ceramics at present, is preparing, is using containing lead base ceramics And in its discarded last handling process, can all endanger environment and human health.Therefore research and develop the meaning depth of Lead-free transparent ceramics Far.2004, M.Kosec et al. reported firsts K0.5Na0.5NbO3-0.2SrTiO3Semitransparent ceramics.Subsequently, Kwok et al. passes through The K that hot pressing sintering method is successively prepared0.48Na0.52Nb1-xBixO3(K0.5Na0.5)1-xLixNb1-xBixO3Ceramics, which is in near-infrared Light area light transmittance all reaches 60%.Recently, Du et al. employs conventional sintering and is prepared for (1-x) K0.5Na0.5NbO3-xSr (Sc0.5Nb0.5)O3During ceramics, wherein x=0.20 (room temperature is pseudo- Emission in Cubic), the ceramics are reached in visible ray iuuminting rate 60%, and with high energy storage characteristic (W=2.48Jcm-3).Research finds that what excellent light transmission was serious reduces ceramics Electric property, especially foundary weight electrical property, What is more so as to loses foundary weight electrical.Therefore, develop a kind of with foundary weight The crystalline ceramics of electrical property has great practical significance.
The content of the invention
The technical problem to be solved be provide it is a kind of have light transmission, high-curie temperature, high-k, The potassium-sodium niobate-based transparent ferroelectric ceramics ceramic material of high remanent polarization, high piezoelectric constant, and the preparation side of the ceramic material Method.
Solving the technical scheme that adopted of above-mentioned technical problem is：The formula of the ceramic material is (1-x) (K0.5Na0.5) NbO3-xCa(Mg1/3Ta2/3)O3, in formula, x represents Ca (Mg1/3Ta2/3)O3Molal quantity, the value of x is 0.02～0.06；The pottery It is that 2563～4190, Curie temperature is 203～361 that transmitance of the porcelain near infrared region is 42%～64%, maximum dielectric constant DEG C, dielectric loss be 0.035～0.04, maximum polarization be 22.2～32.6 μ C/cm2, remanent polarization be 6.6～ 21.6μC/cm2, piezoelectric constant be 28～99pC/N.
In above-mentioned formula, the value of preferred x is 0.02, and transmitance of the ceramics near infrared region be 42%～64%, most It is 32.6 μ C/cm for 361 DEG C, maximum polarization that big dielectric constant is 4190, Curie temperature2, remanent polarization be 21.6 μ C/cm2, piezoelectric constant be 99pC/N.
The preparation method of potassium niobate sodium base leadless transparent ferroelectric ceramics of the present invention is made up of following step：
1st, dispensing
According to (1-x) (K0.5Na0.5)NbO3-xCa(Mg1/3Ta2/3)O3Stoichiometry weigh purity respectively and be more than 99.99% raw material Na2CO3、K2CO3、Nb2O5、CaCO3、MgO、Ta2O5, mix homogeneously；Raw mixture is loaded into nylon tank In, with zirconium ball as abrading-ball, dehydrated alcohol as ball-milling medium, be sufficiently mixed ball milling 18～24 hours, raw material is mixed by separating zirconium ball Thing is dried 12～24 hours at 80～100 DEG C, with mortar grinder, crosses 80 mesh sieves.
2nd, pre-burning
The raw mixture that step 1 is crossed after 80 mesh sieves is placed in alumina crucible, is carried out within 3 hours in 850 DEG C of insulations pre- Burn, naturally cool to room temperature, with mortar grinder, obtain pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is loaded in nylon tank, with zirconium ball as abrading-ball, dehydrated alcohol as ball-milling medium, be sufficiently mixed ball milling 12～ 16 hours, pre-burning powder was dried 12～24 hours at 80～100 DEG C by separating zirconium ball, with mortar grinder, crossed 120 mesh sieves.
4th, pelletize and tabletting
The polyvinyl alcohol water solution that mass fraction is 5%, polyethylene are added in the pre-burning powder crossed after 120 mesh sieves to step 3 The addition of alcohol-water solution for pre-burning silty amount 40%～50%, pelletize are crossed 120～180 mesh sieves, are pressed into circle with tablet machine Column base substrate.
5th, sintering is closed without densification
Cylindric blank is placed on zirconium oxide flat board, zirconium oxide flat board is placed in the closed saggar of aluminium oxide, and in oxygen Change and pre-burning powder is paved with around zirconium flat board, be first warming up to 500 DEG C with 380 minutes, be incubated 2 hours, then with 3 DEG C/min of intensification speed Rate is warming up to 1180～1200 DEG C, sinters 5～15 hours, naturally cools to room temperature.
6th, polish
Ceramics after step 5 is sintered choose one of sample surfaces sand papering of 320 mesh, then use 800 mesh Sand papering, finally the sand paper and diamond polishing with 1500 mesh is thick to 0.5～0.6mm, is wiped over totally with ethanol.
7th, silver ink firing
Ceramic upper and lower surface coating thickness after step 6 polishing is the silver paste of 0.01～0.03mm, is placed in resistance furnace 840 DEG C are incubated 30 minutes, naturally cool to room temperature, and the potassium niobate sodium base leadless for obtaining high remanent polarization and Curie temperature is saturating Bright ferroelectric ceramics.
In above-mentioned steps 5, preferably 1190 DEG C are warming up to 3 DEG C/min of heating rate, sinter 8 hours.
Preparation method of the present invention is simple, reproducible, high yield rate, gained ceramic material have excellent electric property and Certain light transmittance, it is 2563～4190, Ju Liwen that its transmitance near infrared region is 42%～64%, maximum dielectric constant It is that 0.035～0.04, maximum polarization is 22.2～32.6 μ C/cm to spend for 203～361 DEG C, dielectric loss2, residual polarization Intensity is 6.6～21.6 μ C/cm2, piezoelectric constant be 28～99pC/N.Ceramic material of the present invention optically isotropism, reality With property it is strong, be readily produced, electric property and optical property can be taken into account, be a kind of Lead-free transparent ferroelectric ceramics of function admirable.
Description of the drawings
Fig. 1 is the XRD figure of potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material prepared by embodiment 1～3.
Fig. 2 is the light transmittance figure of the standby potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material of embodiment 1～3.
Fig. 3 is dielectric constant of the potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material of the preparation of embodiment 1～3 under 1MHz Vary with temperature graph of a relation.
Fig. 4 is Curie temperature of the potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material of the preparation of embodiment 1～3 under 1MHz With maximum dielectric constant with x values variation relation figure.
Fig. 5 is the ferroelectric hysteresis loop collection of illustrative plates of potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material prepared by embodiment 1～3.
Fig. 6 is that the dielectric loss of potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material for preparing of embodiment 1～3, piezoelectricity are normal The variation relation figure of number, maximum polarization and remanent polarization with x values.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to These embodiments.
Embodiment 1
1st, dispensing
According to 0.98 (K0.5Na0.5)NbO3-0.02Ca(Mg1/3Ta2/3)O3Stoichiometry weigh purity respectively and be 99.99% Na2CO32.6593g, purity are 99.99% K2CO33.4676g, purity are 99.99% Nb2O5 13.3382g, purity are 99.99% CaCO30.2050g, purity be 99.99% MgO 0.0302g, purity be 99.99% Ta2O50.3017g, mix homogeneously load raw mixture in nylon tank, with zirconium ball as abrading-ball, dehydrated alcohol For ball-milling medium, dehydrated alcohol is 1 with the mass ratio of raw mixture:1.2, with 401 revs/min of ball mill ball milling 24 hours, Separating zirconium ball, raw mixture is placed in drying baker and is dried 24 hours at 80 DEG C, with mortar grinder 30 minutes, crosses 80 mesh Sieve.
2nd, pre-burning
The raw mixture that step 1 is crossed after 80 mesh sieves is placed in alumina crucible, is compacted with Achatess rod so as to be compacted close Spend for 1.5g/cm3, add a cover, be placed in resistance furnace, 850 DEG C of pre-burnings 3 hours are warming up to 3 DEG C/min of heating rate, it is natural Room temperature is cooled to, is come out of the stove, with mortar grinder 10 minutes, obtain pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is loaded in nylon tank, with zirconium ball as abrading-ball, dehydrated alcohol as ball-milling medium, dehydrated alcohol and pre-burning powder Mass ratio be 1:1.2, with 401 revs/min of ball mill ball milling 16 hours, separating zirconium ball is placed in pre-burning powder in drying baker It is dried 24 hours at 80 DEG C, with mortar grinder 10 minutes, crosses 120 mesh sieves.
4th, pelletize and tabletting
The polyvinyl alcohol water solution that mass fraction is 5%, polyethylene are added in the pre-burning powder crossed after 120 mesh sieves to step 3 The addition of alcohol-water solution for pre-burning silty amount 50%, pelletize are crossed 180 mesh sieves, make spherical powder, spherical powder is put into In the stainless steel mould of a diameter of 15mm, it is 1.5mm's that thickness is compressed under the pressure of 300MPa with powder compressing machine Cylindric blank.
5th, sintering is closed without densification
Cylindric blank is placed on zirconium oxide flat board, zirconium oxide flat board is placed in the closed saggar of aluminium oxide, and in oxygen Change and pre-burning powder is paved with around zirconium flat board, be first warming up to 500 DEG C with 380 minutes, be incubated 2 hours, then with 3 DEG C/min of intensification speed Rate is warming up to 1190 DEG C, sinters 8 hours, naturally cools to room temperature with stove.
6th, polish
Ceramics after step 5 is sintered choose one of sample surfaces sand papering of 320 mesh, then use 800 mesh Sand papering, finally the sand paper and diamond polishing with 1500 mesh is thick to 0.5mm, is wiped over totally with ethanol.Using Japan's reason Learning MiniFlex600 types diffractometer carries out XRD tests, is carried out using UV-3600 type UV, visible light near infrared light spectrophotometers Optical transmittance is tested, and as a result sees Fig. 1～2.
7th, silver ink firing
Silver paste of the ceramic upper and lower surface coating thickness after step 6 polishing for 0.02mm, is placed in 840 DEG C of guarantors in resistance furnace Temperature 30 minutes, naturally cools to room temperature, is prepared into potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material.Using Agilient4980A type precise impedance analysers and AixACCT-TF2000 sections electric parameter tester are respectively to ceramic material Dielectric properties and ferroelectric properties are tested, and as a result see Fig. 3～6.
Embodiment 2
In the batching step 1 of the present embodiment, according to 0.96 (K0.5Na0.5)NbO3-0.04Ca(Mg1/3Ta2/3)O3Chemistry meter Amount weighs the Na that purity is 99.99% respectively2CO32.5869g, purity are 99.99% K2CO33.3733g, purity be 99.99% Nb2O512.9754g, purity are 99.99% CaCO30.4072g, purity are 99.99% MgO 0.0601g, purity are 99.99% Ta2O50.5992g, other steps are same as Example 1, are prepared into potassium-sodium niobate-based nothing Lead transparent ferroelectric ceramics ceramic material.
Embodiment 3
In the batching step 1 of the present embodiment, according to 0.94 (K0.5Na0.5)NbO3-0.06Ca(Mg1/3Ta2/3)O3Chemistry meter Amount weighs the Na that purity is 99.99% respectively2CO32.5156g, purity are 99.99% K2CO33.2803g, purity be 99.99% Nb2O512.6175g, purity are 99.99% CaCO30.6065g, purity are 99.99% MgO 0.0895g, purity are 99.99% Ta2O50.8926g, other steps are same as Example 1, are prepared into potassium-sodium niobate-based nothing Lead transparent ferroelectric ceramics ceramic material.
As seen from Figure 1, the ceramic material that prepared by embodiment 1～3 is pure perovskite structure.From Figure 2 it can be seen that embodiment 1～3 ceramic material for preparing is presented certain light transmission, its near infrared region light transmittance up to 42%～64%.By Fig. 3～ 6 is visible, the standby ceramic material maximum dielectric constant of embodiment 1～3, Curie temperature, dielectric loss remanent polarization and piezoelectricity Constant is reduced with the increase of x, and when wherein x values are 0.02, the electric property of the ceramic material is optimal, its maximum dielectric Constant (εm) for 4190, Curie temperature (Tm) for 361 DEG C, dielectric loss (tan δ) be 0.04, maximum polarization (Pm) for 32.6 μC/cm2, remanent polarization (Pr) for 21.6 μ C/cm2, piezoelectric constant (d33) for 99pC/N.

Claims (4)

1. the potassium niobate sodium base leadless transparent ferroelectric ceramics of a kind of high remanent polarization and Curie temperature, it is characterised in that：Should The formula of ceramic material is (1-x) (K0.5Na0.5)NbO3-xCa(Mg1/3Ta2/3)O3, in formula, x represents Ca (Mg1/3Ta2/3)O3Rub That number, the value of x is 0.02～0.06；Transmitance of the ceramics near infrared region is that 42%～64%, maximum dielectric constant is 2563～4190, Curie temperature be 203～361 DEG C, dielectric loss be 0.035～0.04, maximum polarization be 22.2～ 32.6μC/cm2, remanent polarization be 6.6～21.6 μ C/cm2, piezoelectric constant be 28～99pC/N.
2. the potassium niobate sodium base leadless transparent ferroelectric ceramics of high remanent polarization according to claim 1 and Curie temperature Porcelain, it is characterised in that：The value of the x is 0.02, and transmitance of the ceramics near infrared region is 42%～64%, maximum dielectric It is 32.6 μ C/cm for 361 DEG C, maximum polarization that constant is 4190, Curie temperature2, remanent polarization be 21.6 μ C/cm2、 Piezoelectric constant is 99pC/N.
3. the potassium niobate sodium base leadless transparent ferroelectric ceramics of the high remanent polarization and Curie temperature described in a kind of claim 1 Preparation method, it is characterised in that it is made up of following step：
(1) dispensing
According to (1-x) (K0.5Na0.5)NbO3-xCa(Mg1/3Ta2/3)O3Stoichiometry weigh purity respectively more than 99.99% Raw material Na2CO3、K2CO3、Nb2O5、CaCO3、MgO、Ta2O5, mix homogeneously；Raw mixture is loaded in nylon tank, with zirconium ball Be ball-milling medium for abrading-ball, dehydrated alcohol, be sufficiently mixed ball milling 18～24 hours, separating zirconium ball, by raw mixture 80～ It is dried 12～24 hours at 100 DEG C, with mortar grinder, crosses 80 mesh sieves；
(2) pre-burning
The raw mixture that step (1) is crossed after 80 mesh sieves is placed in alumina crucible, pre-burning is carried out within 3 hours in 850 DEG C of insulations, Room temperature is naturally cooled to, with mortar grinder, pre-burning powder is obtained；
(3) secondary ball milling
By pre-burning powder load nylon tank in, with zirconium ball as abrading-ball, dehydrated alcohol as ball-milling medium, be sufficiently mixed ball milling 12～16 little When, pre-burning powder is dried 12～24 hours at 80～100 DEG C by separating zirconium ball, with mortar grinder, crosses 120 mesh sieves；
(4) pelletize and tabletting
The polyvinyl alcohol water solution that mass fraction is 5%, polyvinyl alcohol are added in the pre-burning powder crossed after 120 mesh sieves to step (3) The addition of aqueous solution for pre-burning silty amount 40%～50%, pelletize are crossed 120～180 mesh sieves, are pressed into cylinder with tablet machine Shape base substrate；
(5) sintering is closed without densification
Cylindric blank is placed on zirconium oxide flat board, zirconium oxide flat board is placed in the closed saggar of aluminium oxide, and in zirconium oxide Pre-burning powder is paved with around flat board, first 500 DEG C was warming up to 380 minutes, be incubated 2 hours, then with 3 DEG C/min of heating rate liter Temperature is sintered 5～15 hours, naturally cools to room temperature to 1180～1200 DEG C；
(6) polish
Ceramics after step (5) is sintered choose one of sample surfaces sand papering of 320 mesh, then use 800 purposes Sand papering, finally the sand paper and diamond polishing with 1500 mesh is thick to 0.5～0.6mm, is wiped over totally with ethanol；
(7) silver ink firing
Ceramic upper and lower surface coating thickness after step (6) polishing is the silver paste of 0.01～0.03mm, is placed in 840 in resistance furnace DEG C insulation 30 minutes, naturally cool to room temperature, the potassium niobate sodium base leadless for obtaining high remanent polarization and Curie temperature is transparent Ferroelectric ceramics.
4. the preparation method of potassium niobate sodium base leadless transparent ferroelectric ceramics according to claim 3, it is characterised in that：In step Suddenly in (5), cylindric blank is placed on zirconium oxide flat board, zirconium oxide flat board is placed in the closed saggar of aluminium oxide, and in oxygen Change and pre-burning powder is paved with around zirconium flat board, be first warming up to 500 DEG C with 380 minutes, be incubated 2 hours, then with 3 DEG C/min of intensification speed Rate is warming up to 1190 DEG C, sinters 8 hours, naturally cools to room temperature with stove.
CN201611266530.6A 2016-12-31 2016-12-31 Potassium niobate sodium base leadless transparent ferroelectric ceramics of high remanent polarization and Curie temperature and preparation method thereof Expired - Fee Related CN106588011B (en)

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CN110981476A (en) * 2019-12-17 2020-04-10 西安工业大学 Potassium sodium niobate-based transparent ceramic material and preparation method thereof
CN111302798A (en) * 2020-02-25 2020-06-19 西安工业大学 Lanthanum oxide doped modified potassium-sodium niobate-based transparent ceramic and preparation method thereof
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CN112510171A (en) * 2019-09-13 2021-03-16 株式会社东芝 Composite oxide, active material composite material, electrode, battery pack, and vehicle
CN110981476A (en) * 2019-12-17 2020-04-10 西安工业大学 Potassium sodium niobate-based transparent ceramic material and preparation method thereof
CN111302798A (en) * 2020-02-25 2020-06-19 西安工业大学 Lanthanum oxide doped modified potassium-sodium niobate-based transparent ceramic and preparation method thereof
CN111302798B (en) * 2020-02-25 2022-02-22 西安工业大学 Lanthanum oxide doped modified potassium-sodium niobate-based transparent ceramic and preparation method thereof
CN113121226A (en) * 2021-04-30 2021-07-16 桂林电子科技大学 Optical dielectric ferroelectric ceramic material and preparation method and application thereof

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