CN106588011B - Potassium niobate sodium base leadless transparent ferroelectric ceramics of high remanent polarization and Curie temperature and preparation method thereof - Google Patents

Potassium niobate sodium base leadless transparent ferroelectric ceramics of high remanent polarization and Curie temperature and preparation method thereof Download PDF

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CN106588011B
CN106588011B CN201611266530.6A CN201611266530A CN106588011B CN 106588011 B CN106588011 B CN 106588011B CN 201611266530 A CN201611266530 A CN 201611266530A CN 106588011 B CN106588011 B CN 106588011B
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curie temperature
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remanent polarization
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CN106588011A (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 potassium niobate sodium base leadless transparent ferroelectric ceramics of a kind of high remanent polarization and Curie temperature and preparation method thereof, the general formula of the ceramic material is (1 x) (K0.5Na0.5)NbO3‑xCa(Mg1/3Ta2/3)O3, the value of x is 0.02~0.06, is prepared by high temperature solid-state method.Preparation method of the present invention is simple, reproducible, high yield rate, gained ceramic material has excellent electric property and certain light transmittance, and the transmitance near infrared region is 42%~64%, dielectric constant is 2563~4190, Curie temperature is 203~361 DEG C, dielectric loss is 0.035~0.04, polarization intensity is 22.2~32.6 μ C/cm2, remanent polarization be 6.6~21.6 μ C/cm2, piezoelectric constant be 28~99pC/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 The preparation method of potassium sodium base Lead-free transparent ferroelectric ceramics and the ceramics.
Background technology
Today's society, piezoelectricity, ferroelectric material are used widely as a kind of important functional material on photoelectric device. The advantages that performance that ceramic piezoelectric material is stablized with it, low production cost as piezoelectric material important component.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 the critical material in indispensable following optical computer technology and modern advanced.
The transparent ferroelectric ceramics applied at present is mainly lead zirconate titanate (PZT) base ceramics, and ceramics containing lead base are being prepared, used And in its discarded last handling process, it can all endanger environment and human health.Therefore the meaning of research and development Lead-free transparent ceramics is deep Far.2004, M.Kosec et al. reported K for the first time0.5Na0.5NbO3-0.2SrTiO3Semitransparent ceramics.Then, Kwok et al. passes through The K that hot pressing sintering method is successively prepared0.48Na0.52Nb1-xBixO3(K0.5Na0.5)1-xLixNb1-xBixO3Ceramics, 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)O3When ceramics, wherein x=0.20 (room temperature is pseudo- cubic phase), which reaches in visible ray iuuminting rate 60%, and with high energy storage characteristic (W=2.48Jcm-3).The study found that excellent translucency is serious to reduce ceramics Electric property, especially weight electrical property, What is more, it is made to lose weight electrical.Therefore, exploitation is a kind of has weight The crystalline ceramics of electrical property has great practical significance.
Invention content
The technical problems to be solved by the invention be to provide it is a kind of have translucency, high-curie temperature, high-k, High remanent polarization, the potassium-sodium niobate-based transparent ferroelectric ceramics ceramic material of high piezoelectric constant and the preparation side of the ceramic material Method.
Technical solution is used by solving above-mentioned technical problem：The general formula of the ceramic material is (1-x) (K0.5Na0.5) NbO3-xCa(Mg1/3Ta2/3)O3, x represents Ca (Mg in formula1/3Ta2/3)O3Molal quantity, the value of x is 0.02~0.06；The pottery Transmitance of the porcelain near infrared region is 42%~64%, dielectric constant is 2563~4190, Curie temperature is 203~361 DEG C, is situated between Electrical loss is 0.035~0.04, polarization intensity is 22.2~32.6 μ C/cm2, remanent polarization be 6.6~21.6 μ C/cm2、 Piezoelectric constant is 28~99pC/N.
In above-mentioned general formula, preferably the value of x is 0.02, and transmitance of the ceramics near infrared region is 42%~64%, is situated between Electric constant is 4190, Curie temperature is 361 DEG C, polarization intensity is 32.6 μ C/cm2, remanent polarization be 21.6 μ C/cm2, pressure Electric constant is 99pC/N.
The preparation method of potassium niobate sodium base leadless transparent ferroelectric ceramics of the present invention is made 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, it is uniformly mixed；Raw mixture is packed into nylon tank In, it is ball-milling medium by abrading-ball, absolute ethyl alcohol of zirconium ball, is sufficiently mixed ball milling 18~24 hours, separating zirconium ball mixes raw material Object is 12~24 hours dry at 80~100 DEG C, 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 carried out within 3 hours in 850 DEG C of heat preservations pre- It burns, cooled to room temperature with mortar grinder, 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, be sufficiently mixed ball milling 12~ 16 hours, separating zirconium ball was 12~24 hours dry at 80~100 DEG C by pre-burning powder, with mortar grinder, crossed 120 mesh sieve.
4th, granulation and tabletting
It is crossed to step 3 and the polyvinyl alcohol water solution that mass fraction is 5%, polyethylene is added in the pre-burning powder after 120 mesh sieve The addition of alcohol solution is the 40%~50% of pre-burning silty amount, is granulated, and crosses 120~180 mesh sieve, circle is pressed into tablet press machine Column green body.
5th, sintering is closed without densification
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 1180~1200 DEG C, is sintered 5~15 hours, cooled to room temperature.
6th, it polishes
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 to 0.5~0.6mm thickness with the sand paper of 1500 mesh and diamond polishing.
7th, silver ink firing
The silver paste that ceramic upper and lower surface coating thickness after step 6 polishing is 0.01~0.03mm, is placed in resistance furnace 840 DEG C keep the temperature 30 minutes, cooled 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 5,1190 DEG C preferably are warming up to 3 DEG C/min of heating rate, is sintered 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, the transmitance near infrared region is 42%~64%, dielectric constant is 2563~4190, Curie temperature is 203~361 DEG C, dielectric loss be 0.035~0.04, polarization intensity is 22.2~32.6 μ C/cm2, remanent polarization 6.6 ~21.6 μ C/cm2, piezoelectric constant be 28~99pC/N.Ceramic material of the present invention optically isotropism, highly practical, easy In production, electric property and optical property can be taken into account, is a kind of Lead-free transparent ferroelectric ceramics of function admirable.
Description of the drawings
Fig. 1 is the XRD diagram of potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material prepared by Examples 1 to 3.
Fig. 2 is the light transmittance figure of the standby potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material of Examples 1 to 3.
Fig. 3 is dielectric constant of the potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material of Examples 1 to 3 preparation under 1MHz Vary with temperature relational graph.
Fig. 4 is Curie temperature of the potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material of Examples 1 to 3 preparation under 1MHz With maximum dielectric constant with the variation relation figure of x values.
Fig. 5 is the ferroelectric hysteresis loop collection of illustrative plates of potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material prepared by Examples 1 to 3.
Fig. 6 is that dielectric loss, the piezoelectricity of potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material prepared by Examples 1 to 3 are normal Number, maximum polarization and remanent polarization with x values variation relation figure.
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, the K that purity is 99.99%2CO33.4676g, the Nb that purity is 99.99%2O5 13.3382g, the CaCO that purity is 99.99%3MgO 0.0302g that 0.2050g, purity are 99.99%, purity are 99.99% Ta2O50.3017g is uniformly mixed, raw mixture is fitted into nylon tank, using zirconium ball as abrading-ball, absolute ethyl alcohol For ball-milling medium, the mass ratio of absolute ethyl alcohol and raw mixture is 1:1.2, with 401 revs/min of ball mill ball milling 24 hours, Separating zirconium ball, raw mixture is placed in drying box at 80 DEG C 24 hours dry, 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, and 850 DEG C of pre-burnings 3 hours are warming up to 3 DEG C/min of heating rate, natural It is cooled to room temperature, comes out of the stove, with mortar grinder 10 minutes, obtain pre-burning powder.
3rd, secondary ball milling
Pre-burning powder is fitted into nylon tank, is ball-milling medium, absolute ethyl alcohol and pre-burning powder by abrading-ball, absolute ethyl alcohol of zirconium ball Mass ratio be 1:1.2, with 401 revs/min of ball mill ball milling 16 hours, pre-burning powder is placed in drying box by separating zirconium ball Dry 24 hours at 80 DEG C, with mortar grinder 10 minutes, 120 mesh sieve is crossed.
4th, granulation and tabletting
It is crossed to step 3 and the polyvinyl alcohol water solution that mass fraction is 5%, polyethylene is added in the pre-burning powder after 120 mesh sieve The addition of alcohol solution is the 50% of pre-burning silty amount, is granulated, and crosses 180 mesh sieve, spherical powder is made, spherical powder is put into In the stainless steel mould of a diameter of 15mm, it is 1.5mm's to be compressed into thickness under the pressure of 300MPa with powder compressing machine Cylindric blank.
5th, sintering is closed without densification
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 1190 DEG C, is sintered 8 hours, with stove cooled to room temperature.
6th, it polishes
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 to 0.5mm thickness with the sand paper of 1500 mesh and diamond polishing.It is managed using Japan It learns MiniFlex600 types diffractometer and carries out XRD tests, carried out using UV-3600 type UV, visible light near infrared lights spectrophotometer Optical transmittance is tested, the result is shown in Figure 1~2.
7th, silver ink firing
The silver paste that ceramic upper and lower surface coating thickness after step 6 polishing is 0.02mm is placed in 840 DEG C of guarantors in resistance furnace Temperature 30 minutes, cooled to room temperature is prepared into potassium niobate sodium base leadless transparent ferroelectric ceramics ceramic material.Using Agilient4980A type precise impedance analyzers 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, the K that purity is 99.99%2CO33.3733g, purity be 99.99% Nb2O512.9754g, the CaCO that purity is 99.99%30.4072g, the MgO that purity is 99.99% 0.0601g, the Ta that purity is 99.99%2O50.5992g, 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, the K that purity is 99.99%2CO33.2803g, purity be 99.99% Nb2O512.6175g, the CaCO that purity is 99.99%30.6065g, the MgO that purity is 99.99% 0.0895g, the Ta that purity is 99.99%2O50.8926g, 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 Examples 1 to 3 is pure perovskite structure.From Figure 2 it can be seen that embodiment 1~3 prepare ceramic material certain translucency is presented, near infrared region light transmittance up to 42%~64%.By Fig. 3~ 6 as it can be seen that standby ceramic material maximum dielectric constant, Curie temperature, dielectric loss remanent polarization and the piezoelectricity of Examples 1 to 3 Constant is reduced with the increase of x, and when wherein x values are 0.02, the electric property of the ceramic material is best, maximum dielectric Constant (εm) it is 4190, Curie temperature (Tm) be 361 DEG C, dielectric loss (tan δ) is 0.04, maximum polarization (Pm) it is 32.6 μC/cm2, remanent polarization (Pr) it is 21.6 μ C/cm2, piezoelectric constant (d33) it is 99pC/N.

Claims (4)

1. a kind of potassium niobate sodium base leadless transparent ferroelectric ceramics of high remanent polarization and Curie temperature, it is characterised in that：It should The general formula of ceramic material is (1-x) (K0.5Na0.5)NbO3-xCa(Mg1/3Ta2/3)O3, x represents Ca (Mg in formula1/3Ta2/3)O3Rub That number, the value of x is 0.02~0.06；Transmitance of the ceramics near infrared region is 42%~64%, dielectric constant 2563 ~4190, Curie temperature is 203~361 DEG C, dielectric loss is 0.035~0.04, polarization intensity is 22.2~32.6 μ C/cm2、 Remanent polarization is 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%, dielectric constant It it is 361 DEG C for 4190, Curie temperature, polarization intensity is 32.6 μ C/cm2, remanent polarization be 21.6 μ C/cm2, piezoelectric constant For 99pC/N.
3. a kind of potassium niobate sodium base leadless transparent ferroelectric ceramics of high remanent polarization described in claim 1 and Curie temperature Preparation method, it is characterised in that it is made of following step：
(1) dispensing
According to (1-x) (K0.5Na0.5)NbO3-xCa(Mg1/3Ta2/3)O3Stoichiometry respectively weigh purity more than 99.99% Raw material Na2CO3、K2CO3、Nb2O5、CaCO3、MgO、Ta2O5, it is uniformly mixed；Raw mixture is fitted into nylon tank, with zirconium ball Be ball-milling medium for abrading-ball, absolute ethyl alcohol, be sufficiently mixed ball milling 18~24 hours, separating zirconium ball, by raw mixture 80~ It is 12~24 hours dry at 100 DEG C, with mortar grinder, cross 80 mesh sieve；
(2) pre-burning
Raw mixture step (1) crossed after 80 mesh sieve is placed in alumina crucible, and pre-burning is carried out within 3 hours in 850 DEG C of heat preservations, Cooled to room temperature with mortar grinder, 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 12~16 When, separating zirconium ball is 12~24 hours dry at 80~100 DEG C by pre-burning powder, with mortar grinder, crosses 120 mesh sieve；
(4) granulation and tabletting
It is crossed to step (3) and the polyvinyl alcohol water solution that mass fraction is 5%, polyvinyl alcohol is added in the pre-burning powder after 120 mesh sieve The addition of aqueous solution is the 40%~50% of pre-burning silty amount, is granulated, and crosses 120~180 mesh sieve, cylinder is pressed into tablet press machine Shape green body；
(5) sintering is closed without densification
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 5~15 hours, cooled to room temperature to 1180~1200 DEG C；
(6) it polishes
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 purposes Sand paper is polished, and is finally wiped over totally with alcohol to 0.5~0.6mm thickness with the sand paper of 1500 mesh and diamond polishing；
(7) silver ink firing
The silver paste that ceramic upper and lower surface coating thickness after step (6) polishing is 0.01~0.03mm, is placed in 840 in resistance furnace DEG C heat preservation 30 minutes, cooled 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 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 1190 DEG C, is sintered 8 hours, with stove cooled to room temperature.
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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