CN102241511B - Ferroelectric-antiferroelectric (FE-AFE) phase change pyroelectric ceramic material, ceramic element thereof and preparation methods thereof - Google Patents

Ferroelectric-antiferroelectric (FE-AFE) phase change pyroelectric ceramic material, ceramic element thereof and preparation methods thereof Download PDF

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CN102241511B
CN102241511B CN 201010170613 CN201010170613A CN102241511B CN 102241511 B CN102241511 B CN 102241511B CN 201010170613 CN201010170613 CN 201010170613 CN 201010170613 A CN201010170613 A CN 201010170613A CN 102241511 B CN102241511 B CN 102241511B
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董显林
张红玲
陈学锋
曹菲
王根水
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention which relates to an FE-AFE phase change pyroelectric ceramic material belongs to the field of pyroelectric ceramic. The invention discloses the FE-AFE phase change pyroelectric ceramic material, a pyroelectric ceramic element and preparation methods of the material and the element. Chemical components of the ceramic material accord with a general chemical formula of (Pb1-3x/2Lax)(ZryTizSn1-y-z)O3, wherein x is more than 0 and equal to or less than 0.025, y is from 0.38 to 0.46, and z is from 0.14 to 0.18; and the ceramic material is in a ferroelectric phase at room temperature and can generate an FE-AFE phase change with the temperature change with or without an extra electric field. The pyroelectric ceramic element has a large polarized change with the FE-AFE phase change after being polarized or under the effect of a direct current bias, so a large pyroelectric response is obtained, a pyroelectric coefficient is 2-4 times more than traditional pyroelectric coefficients, and heat stagnation substantially does not exist, so the pyroelectric ceramic element can be used in the uncooled infrared detection technology and the fields of heat-electrical energy transformation and the like.

Description

A kind of ferroelectric-the antiferroelectric phase heating releases electroceramics material, ceramic component and preparation method thereof
Technical field
The invention belongs to the pyroelectric ceramics field, relate to a kind of phase transformation pyroelectric ceramics, relate in particular to a kind of ferroelectric-antiferroelectric (FE-AFE) phase transformation pyroelectric ceramic material and ceramic component.
Background technology
Pyroelectric effect can be directly used in the aspects such as infrared acquisition, heat-electric energy conversion, heat joule application.Owing to have easy to prepare, with low cost, steady performance, pyroelectric ceramic material all is widely used in dual-use field.Use at present more pyroelectric ceramics roughly can be divided into two large classes: a class is traditional pyroelectric ceramics, such as Pb (Zr xTi 1-x) O 3(PZT) the base pottery utilizes its variation with temperature that polarizes away from transformation temperature the time, is operated in Curie temperature (T c) below; Another kind of is the phase transformation pyroelectricity material, such as (Ba xSr 1-x) TiO 3(BST) base, Pb (Sc 0.5Ta 0.5) O 3(PST) base is ceramic, mainly utilizes near the induction pyroelectric effect of the variation generation of the dielectric constant with temperature of phase transformation, is operated in T cNear, need outer Electric Field Biased.In addition, has the ferroelectric tripartite phase (F of low temperature-high temperature R (LT)-F R (HT)) phase transformation rich zirconium PZT base pottery because pyroelectric coefficient is higher, during phase transformation material specific inductivity almost constant, need not the advantage such as repolarization, also obtained broad research.
By means such as ion doping, process modification, the pyroelectric property of ferroelectric ceramic(s) is improved.S.T.Liu etc. (Ferroelectrics, 3,281 (1972) .) have prepared the PZT pottery of mixing La, and than other material, its pyroelectric coefficient can bring up to 18 * 10 -8Ccm -2K -1N.M.Shorrocks etc. (Ferroelectrics, 106,387 (1990) .) have studied the induction pyroelectric response of PST pottery under the bias voltage, and the pyroelectric coefficient peak value is about 60 * 10 near ferroelectric-para-electric (FE-PE) phase transformation -8Ccm -2K -1R.M.Henson etc. (Phys.Stat.Sol. (a), 46,511 (1978) .) form by adjusting, with PbTiO 3-PbZrO 3-Pb (Fe 1/2Ta 1/2) O 3(PZFNT) three component system F R (LT)-F R (HT)The heat stagnation of phase transformation has been reduced to 0.5 ℃.1992, (the Proceedings of the 8 such as B.M.Kulwicki ThIEEE ISAF, 90,1 (1992) .) performance of pyroelectricity material commonly used has been carried out statistical study, wherein the pyroelectric coefficient of BST pottery can reach 70 * 10 -8Ccm -2K -1, this material is a kind of important commercial pyroelectric ceramics at present.
Energy transformation when utilizing phase transformation and electrostrictive effect, the basic pottery of the PZT of Sn modification (PZST) is widely used in the fields such as energy storage capacitor, underwater acoustic transducer.For a long time, the transformation behavior of PZST base pottery carried out broad research.Recently, the ferroelectric phase (FE that exists a kind of electric field to induce in the PZST base pottery that the researchist finds in the La modification IN)-AFE phase transformation (Appl.Phys.Lett.87,192904 (2005) .).We are to Pb 0.955La 0.03(Zr 0.42Ti 0.18Sn 0.40) O 3The pyroelectric response of pottery is studied, and finds that pottery is at FE INPyroelectric coefficient can be up to 160 * 10 during-AFE phase transformation -8Ccm -2K -1But because this phase transformation is that electric field is induced generation, electric field tends to stablize FE INPhase, and temperature tends to stablize the AFE phase, heat stagnation very large (＞30 ℃) during these pottery heating and cooling has limited its practical application (Appl.Phys.Lett.94,252902 (2009) .).The present invention is by adjustment of formula, and the stupalith that obtains is induced FE with the electric field of the stupalith of reporting before IN-AFE phase-change mechanism is different, FE-AFE phase transformation in this pottery is intrinsic, only need be temperature-induced, and the heating and cooling transformation temperature approaches, substantially do not have heat stagnation, practical application in fields such as Uncooled infrared detection technology or heat-electric energy conversion has important value to pottery for this.
Summary of the invention
The purpose of this invention is to provide a kind of ferroelectric-antiferroelectric (FE-AFE) phase transformation pyroelectric ceramic material, to overcome the deficiencies in the prior art.
In order to solve the problems of the technologies described above, the invention discloses a kind of ferroelectric-antiferroelectric (FE-AFE) phase transformation pyroelectric ceramic material and preparation method thereof, polarization method and pyroelectric property measuring method.By adjustment of formula and biasing selected, regulate pyroelectric response temperature and sensitivity, expanded the high pyroelectric response stupalith of a kind of new FE-AFE inversion of phases, for infrared thermal release electric Detection Techniques, heat-electric energy conversion etc. provide a kind of new candidate material.
Technical scheme of the present invention is as follows:
A kind of ferroelectric-antiferroelectric (FE-AFE) phase transformation pyroelectric ceramic material, its chemical ingredients meets chemical general formula (Pb 1-3x/2La x) (Zr yTi zSn 1-y-z) O 3, wherein, 0＜x≤0.025, y=0.38～0.46, z=0.14～0.18; The part in the element lower right corner represents mol ratio in the described chemical general formula.
Preferably, to release the chemical general formula of electroceramics material be (Pb in ferroelectric-antiferroelectric phase heating 1-3x/2La x) (Zr yTi zSn 1-y-z) O 3, wherein, x=0.005～0.025, y=0.42～0.44, z=0.16～0.18;
Described phase transformation pyroelectric ceramic material at room temperature is ferroelectric phase, having or not in the situation of extra electric field, described phase transformation pyroelectric ceramic material vary with temperature all can occur reversible ferroelectric-antiferroelectric phase transformation.
Described pyroelectric ceramic material ferroelectric-antiferroelectric (FE-AFE) become the intrinsic phase transformation and the phase transformation of non-electric field induction type mutually, only needs temperature-induced;
Different according to forming, described pyroelectric ceramic material when temperature is 80-145 ℃, occur reversible ferroelectric-antiferroelectric phase transformation.
A kind of pyroelectric ceramics element, for according to described ferroelectric-the antiferroelectric phase heating releases electroceramics material and makes.
Described pyroelectric ceramics element is after polarization is processed, and near the FE-AFE transformation temperature, pyroelectric coefficient is 140 * 10 -8-460 * 10 -8Ccm -2K -1
Preferably, described pyroelectric ceramics element is after polarization is processed, and near the FE-AFE transformation temperature, pyroelectric coefficient is 200 * 10 -8-460 * 10 -8Ccm -2K -1
Described pyroelectric ceramics element is under the direct-current biasing effect, and near the FE-AFE transformation temperature, pyroelectric coefficient is 40 * 10 -8-230 * 10 -8Ccm -2K -1
Described pyroelectric ceramics element is under the direct-current biasing effect, and there is not heat stagnation substantially in the heat stagnation during heating and cooling≤3.5 ℃.
This shows that this pyroelectric ceramics element follows the FE-AFE phase transformation to have larger polarization to change, and can obtain larger pyroelectric response after polarization is processed or under the direct-current biasing effect.
Of the present invention ferroelectric-the antiferroelectric phase heating releases the preparation method of electroceramics material, comprises the steps:
(a) with Pb 3O 4, ZrO 2, TiO 2, SnO 2And La 2O 3Powder be raw material, according to (Pb 1-3x/2La x) (Zr yTi zSn 1-y-z) O 3The stoichiometric ratio preparation of corresponding element, mix with the wet ball-milling method; Briquetting after the oven dry obtains ceramic powder behind the sintering.
During wet ball-milling method described in the step (a) is mixed, according to raw material: ball: water=1: (1.4～1.8): the mass ratio of (0.7～1.0) mixed 5～7 hours, and wherein ball-milling medium is steel ball, zirconium ball or agate ball, and water is deionized water;
Described sintering condition is incubated 1～3 hour for to rise to 820～880 ℃ with the heat-up rate that is lower than 2 ℃/min.
(b) with the wet ball-milling method fine grinding of the ceramic powder of step (a) gained, add the binding agent granulation after the oven dry, compression moulding after the ageing, the plastic removal that then heats up obtains ceramic body.
In the wet ball-milling method described in the step (b), according to ceramic powder: ball: water=1: (1.6～2.0): the quality of (0.5～0.7) compares fine grinding, so that the particle diameter of ceramic powder is thin and narrowly distributing, wherein ball-milling medium is steel ball, zirconium ball or agate ball, and water is deionized water; The described wet ball-milling method fine grinding time is 20～28 hours, obtains ceramic powder after the fine grinding;
Described binding agent is PVA, and the add-on of its binding agent is 6～8wt.% of ceramic powder weight; Digestion time is 22～26 hours; Described plastic removal carries out under 750～850 ℃.
(c) ceramic body of step (b) gained is put into High Temperature Furnaces Heating Apparatus, cover ceramic body with the described ceramic powder of step (a), obtain described stupalith behind the sintering.
Described sintering condition is incubated 1～2 hour, furnace cooling for to rise to 1260～1360 ℃ with the heat-up rate that is lower than 2 ℃/min.
The preparation method of pyroelectric ceramics element of the present invention comprises the steps:
Electroceramics material is released in ferroelectric-antiferroelectric phase heating be processed into desired size, the screen printing of silver paste, oven dry obtains described pyroelectric ceramics element behind the silver ink firing.
Described silver ink firing condition is 650～750 ℃ of lower insulations 20～40 minutes.
Of the present invention ferroelectric-that the polarization method of electroceramics material is released in the antiferroelectric phase heating is as follows:
In silicone oil, the pyroelectric ceramics element is polarized.
Polarization condition is: polarized electric field intensity is 0.6～3.5kV/mm, and the polarization temperature is between 20～120 ℃, and the polarization time is 10～30 minutes.
The testing method of the pyroelectric coefficient of pyroelectric ceramics element of the present invention comprises the steps:
(a) ceramic component to having polarized, bias voltage is made as 0kV/mm, and Cooling rate is 1～3 ℃/min, measures the pyroelectric response of ceramic component behind the different electric field polarizations.
(b) to polarized ceramics element not, (0～1.5kV/mm), Cooling rate is 1～3 ℃/min, measures the not pyroelectric response of polarized ceramics element under different bias voltages to add different direct-current biasinges.
(c) electric charge of measuring in the alternating temperature process with the quiescent current method discharges, by formula p=I/[A (dT/dt)] calculate its pyroelectric coefficient, estimate its pyroelectric property.
Wherein p is pyroelectric coefficient, and I is the pyroelectricity electric current, and A is electrode area, and T is temperature, and t is the time, and dT/dt is Cooling rate.
The FE-AFE Phase transformation ceramics element that the present invention obtains, behind electric field polarization, near the FE-AFE transformation temperature, pyroelectric coefficient can be up to 140 * 10 -8-460 * 10 -8Ccm -2K -1If do not polarize only biasing, near the FE-AFE transformation temperature, pyroelectric coefficient is also up to 40 * 10 -8-230 * 10 -8Ccm -2K -1, during heating and cooling substantially without heat stagnation.Composition according to the pyroelectric ceramics element is different, and described transformation temperature is 80-145 ℃.FE with prior art IN-AFE phase change type pyroelectric ceramic phase ratio, pyroelectric coefficient higher (than the high 2-4 of traditional pyroelectric coefficient doubly) not only, heat stagnation also significantly reduces, and practical application in fields such as Uncooled infrared detection technology or heat-electric energy conversion has important value to this stupalith for these.
Chemical formula is Pb in pyroelectric ceramic material of the present invention and the prior art 0.955La 0.03(Zr 0.42Ti 0.18Sn 0.40) O 3Stupalith compare, phase-change mechanism is different, pyroelectric coefficient is higher during phase transformation, the heating and cooling transformation temperature approaches, and does not substantially have heat stagnation.Its both concrete mechanism is compared as follows:
In the prior art, chemical formula is Pb 0.955La 0.03(Zr 0.42Ti 0.18Sn 0.40) O 3Stupalith at FE INPyroelectric coefficient can reach 160 * 10 during-AFE phase transformation -8Ccm -2K -1Yet this phase transformation is that electric field is induced just and can be occured.This stupalith at room temperature take AFE mutually as principal phase, to a certain degree AFE and FE two-phase coexistent are arranged simultaneously.AFE-para-electric (PE) and PE-AFE phase transformation only occur in heating and cooling under null field.Only has the electric field of working as near AFE-FE INForward when turning to electric field (0.6kV/mm), stupalith could be induced by electric field and is FE INPhase, and with temperature rising generation FE IN-AFE phase transformation, the larger pyroelectric response of final acquisition.In addition, because electric field tends to stablize FE INPhase, temperature tend to stablize the AFE phase, and the pottery of this kind two-phase coexistent has wider AFE and FE coexistence, the AFE-FE during cooling under outer field action INThe FE of transformation temperature when heating up IN-AFE transformation temperature.Heating and cooling heat stagnation (＞30 ℃) has limited FE greatly INThe practical application of-AFE Phase transformation ceramics.
Of the present invention ferroelectric-antiferroelectric pyroelectric ceramic material, by adjustment of formula, having obtained prima facies is the stupalith of FE phase.Because the La content, the phase of stupalith becomes FE mutually by original AFE with the FE two-phase coexistent under the room temperature, and phase-change mechanism also is different from the electric field of prior art and induces FE IN-AFE phase transformation.FE-AFE phase transformation in this stupalith is intrinsic, no matter has or not extra electric field, only need be temperature-induced, and stupalith varies with temperature, and reversible FE-AFE-PE phase transformation all can occur.To apply electric field and be the variation in order obtaining to polarize, through little electric field polarization or under little direct-current biasing effect, all to obtain larger pyroelectric response, pyroelectric coefficient can be up to 140 * 10 -8-460 * 10 -8Ccm -2K -1Under the direct-current biasing effect, the AFE-FE transformation temperature all slightly was offset to high temperature with the bias voltage increase when FE-AFE transformation temperature was with cooling during intensification, but the heating and cooling transformation temperature is approaching, does not substantially have heat stagnation.
Description of drawings
The ceramic component ferroelectric hysteresis loop at room temperature of Fig. 1 embodiment 1 gained.
The elastivity of the ceramic component of Fig. 2 embodiment 1 gained (1/ ε)-temperature (T) curve.
The ferroelectric hysteresis loop of ceramic component under differing temps of Fig. 3 embodiment 1 gained.
Pyroelectric coefficient one temperature (p-T) curve of the ceramic component of Fig. 4 embodiment 3 gained behind electric field polarization.
Pyroelectric coefficient-temperature (p-T) curve of the ceramic component of Fig. 5 embodiment 3 gained under direct-current biasing.
The p-T curve of the ceramic component of Fig. 6 embodiment 1 gained heating and cooling under direct-current biasing.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used for explanation the present invention and are not used in restriction protection scope of the present invention.
Embodiment 1:
The chemical formula of ferroelectric-antiferroelectric pyroelectric ceramic material is:
Pb 0.97La 0.02(Zr 0.42Ti 0.18Sn 0.40)O 3
(1) forms each constituent Pb in the calculating powder raw material by above-mentioned chemical formula 3O 4, ZrO 2, TiO 2, SnO 2And La 2O 3Quality and press proportion of composing preparation, adopt the wet ball-milling method to mix, according to raw material: ball: the mass ratio mixing of water=1: 1.6: 0.8 6 hours mixes each component.After the oven dry, add the deionized water of the 10wt.% of powder material, at the air atmosphere lower lock block, rise to 850 ℃ with the heat-up rate that is lower than 2 ℃/min, be incubated 2 hours synthetic Pb that consist of 0.97La 0.02(Zr 0.42Ti 0.18Sn 0.40) O 3Ceramic powder.
(2) ceramic powder of step (1) gained is smashed to pieces, cross 30 mesh sieves, finish grinded 24 hours with the wet ball-milling method again, dry the ceramic powder after finish grinding, then add the 7wt.%PVA binding agent of powder weight, granulation, ageing 24 hours is crossed 30 mesh sieves, compression moulding, then heat up at 800 ℃ of lower plastic removals, obtain biscuit of ceramics.
(3) in order to prevent plumbous component volatilization, biscuit of ceramics is put into triple inversion alumina crucibles, with the ceramic powder with same composition base substrate is covered, cover the ground lid, rise to 1340 ℃ with the heat-up rate that is lower than 2 ℃/min, be incubated 1 hour, obtain ceramic material sample behind the furnace cooling.
(4) ceramic material sample that sinters is polished, cleans, oven dry, silk screen printing silver slurry, again oven dry, silver ink firing obtains ceramic component.
(5) in silicone oil, under the room temperature, respectively with 0.6,1 and the polarized electric field intensity of 3kV/mm to the ceramic component 10min that polarizes.
(6) ceramic component of present embodiment has been carried out the test of the pyroelectric property after polarization is processed, test result sees Table 1.
(7) ceramic component of present embodiment has been carried out pyroelectric property under the direct-current biasing effect and the test of heating and cooling heat stagnation, test result sees Table 2.
Fig. 1 is the ceramic component ferroelectric hysteresis loop at room temperature of gained, the 1st, and the first lap loop line, 2 is second loops.Can find out that this ceramic component at room temperature is the FE phase.
Fig. 2 is 1/ ε-T curve of the ceramic component of gained.As seen from the figure, this ceramic component undergoes phase transition near 100 ℃, so this phase transformation only will occur under temperature-induced.
Fig. 3 is the ferroelectric hysteresis loop of gained ceramic component under differing temps, the 1st, and the first lap loop line, 2 is second loops.As seen from the figure, this ceramic component is the FE phase in the time of 100 ℃, is the AFE phase in the time of 110 ℃.
Therefore, but Fig. 2 and Fig. 3 become the FE-AFE phase transformation mutually in conjunction with what occur near in the explanatory view 2 100 ℃.
Fig. 6 is the p-T curve of ceramic component heating and cooling under bias voltage of gained, and the curve that makes progress is the section that heats up, and downward is temperature descending section.As seen from the figure, substantially there is not heat stagnation.
Embodiment 2:
The chemical formula of ferroelectric-antiferroelectric pyroelectric ceramic material is:
Pb 0.9625La 0.025(Zr 0.42Ti 0.18Sn 0.40)O 3
Form the preparation method who repeats embodiment 1 by above-mentioned chemical formula, can obtain high pyroelectric response at lesser temps.
The ceramic component of present embodiment has been carried out the test of the pyroelectric property after polarization is processed, and test result sees Table 1.
The ceramic component of present embodiment has been carried out pyroelectric property under the direct-current biasing effect and the test of heating and cooling heat stagnation, and test result sees Table 2.
After testing, the ceramic component of gained at room temperature is the FE phase, and the phase transformation of this ceramic component only will occur under temperature-induced, generation become mutually the FE-AFE phase transformation.
Embodiment 3:
The chemical formula of ferroelectric-antiferroelectric pyroelectric ceramic material is:
Pb 0.9775La 0.015(Zr 0.42Ti 0.18Sn 0.40)O 3
Form the preparation method who repeats embodiment 1 by above-mentioned chemical formula, and product is tested.
After testing, the ceramic component of gained at room temperature is the FE phase, and the phase transformation of this ceramic component only will occur under temperature-induced, generation become mutually the FE-AFE phase transformation.
The ceramic component of present embodiment has been carried out the test of the pyroelectric property after polarization is processed, and test result sees Table 1, pyroelectricity peak value p MaxSurpass 450 * 10 -8Ccm -2K -1, be 458 * 10 -8Ccm -2K -1
The ceramic component of present embodiment has been carried out pyroelectric property under the direct-current biasing effect and the test of heating and cooling heat stagnation, and test result sees Table 2, p under the bias voltage MaxAlso up to 230 * 10 -8Ccm -2K -1
Fig. 4 is pyroelectric coefficient-temperature (p-T) curve of ceramic component behind electric field polarization of embodiment 3 gained.As seen from the figure, the rear ceramic component of polarization is at 124.5 ℃ of pyroelectricity peak value P MaxCan be up to 458 * 10 -8Ccm -2K -1
Fig. 5 is pyroelectric coefficient-temperature (p-T) curve of ceramic component under direct-current biasing of embodiment 3 gained.As seen from the figure, under the bias voltage ceramic component at 128.5 ℃ of pyroelectricity peak value P MaxAlso can be up to 230 * 10 -8Ccm -2K -1
Embodiment 4:
The chemical formula of ferroelectric-antiferroelectric pyroelectric ceramic material is:
(Pb 0.9925La 0.005)(Zr 0.44Ti 0.16Sn 0.40)O 3
Form the preparation method who repeats embodiment 1 by above-mentioned chemical formula, and product is tested.
After testing, the ceramic component of gained at room temperature is the FE phase, and the phase transformation of this ceramic component only will occur under temperature-induced, generation become mutually the FE-AFE phase transformation.
The ceramic component of present embodiment has been carried out the test of the pyroelectric property after polarization is processed, and test result sees Table 1.
The ceramic component of present embodiment has been carried out pyroelectric property under the direct-current biasing effect and the test of heating and cooling heat stagnation, and test result sees Table 2, and the heating and cooling heat stagnation can be decreased to below 1 ℃, does not substantially have heat stagnation.
Table 1 pottery is T after the 3kV/mm polarization FE-AFEAnd p Max
Sample T FE-AFE(℃) p max(10 -8C·cm -2·K -1)
Embodiment 1 101.1 218
Embodiment 2 81.5 266
Embodiment 3 124.5 458
Embodiment 4 136.0 367
The T of table 2 pottery under bias voltage FE-AFE, p MaxAnd heating and cooling heat stagnation
Sample Bias (kV/mm) T FE-AFE(℃) p max(10 -8C·cm -2·K -1) The heating and cooling heat stagnation (℃)
Embodiment 1 0.6 116.8 79 1.8
Embodiment 2 1 108.2 44 3.5
Embodiment 3 0.2 128.5 230 1.4
Embodiment 4 0.3 143.1 196 0.6

Claims (9)

1. electroceramics material is released in ferroelectric-antiferroelectric phase heating, and its chemical ingredients meets chemical general formula (Pb 1-3x/2La x) (Zr yTi zSn 1-y-z) O 3, 0＜x≤0.025 wherein, y=0.38～0.46, z=0.14～0.18;
Described phase transformation pyroelectric ceramic material at room temperature is ferroelectric phase, having or not in the situation of extra electric field, described phase transformation pyroelectric ceramic material vary with temperature all can occur reversible ferroelectric-antiferroelectric phase transformation.
As claimed in claim 1 ferroelectric-the antiferroelectric phase heating releases the preparation method of electroceramics material, comprises the steps:
(a) with Pb 3O 4, ZrO 2, TiO 2, SnO 2And La 2O 3Powder be raw material, according to (Pb 1-3x/2La x) (Zr yTi zSn 1-y-z) O 3The stoichiometric ratio preparation of corresponding element, mix with the wet ball-milling method; Briquetting after the oven dry obtains ceramic powder behind the sintering;
(b) with the wet ball-milling method fine grinding of the ceramic powder of step (a) gained, add the binding agent granulation after the oven dry, compression moulding after the ageing, the plastic removal that then heats up obtains ceramic body;
(c) ceramic body of step (b) gained is put into High Temperature Furnaces Heating Apparatus, cover ceramic body with the described ceramic powder of step (a), obtain described stupalith behind the sintering.
3. a kind of pyroelectric ceramic material as claimed in claim 1 is applied to uncooled ir pyroelectric detect technology or heat-electric energy conversion field.
4. pyroelectric ceramics element, for according to claim 1 ferroelectric-the antiferroelectric phase heating releases electroceramics material and makes.
5. pyroelectric ceramics element as claimed in claim 4 is characterized in that: described pyroelectric ceramics element is after polarization is processed, and near ferroelectric-antiferroelectric phase temperature, pyroelectric coefficient is 140 * 10 -8-460 * 10 -8Ccm -2K -1
6. pyroelectric ceramics element as claimed in claim 4, it is characterized in that: described pyroelectric ceramics element is under the direct-current biasing effect, and near ferroelectric-antiferroelectric phase temperature, pyroelectric coefficient is 40 * 10 -8-230 * 10 -8Ccm -2K -1
7. such as claim 5 or 6 described pyroelectric ceramics elements, it is characterized in that: described ferroelectric-the antiferroelectric phase temperature is 80-145 ℃.
8. pyroelectric ceramics element as claimed in claim 4 is characterized in that: described pyroelectric ceramics element under the direct-current biasing effect, the heat stagnation during heating and cooling≤3.5 ℃.
9. such as the preparation method of the arbitrary described pyroelectric ceramics element of claim 4-8, comprise the steps:
Machining of Ceramics claimed in claim 1 is become desired size, the screen printing of silver paste, oven dry obtains described pyroelectric ceramics element behind the silver ink firing.
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