CN106365636A - High-Curie-temperature strontium-barium niobate pyroelectric ceramic material and preparation method thereof - Google Patents
High-Curie-temperature strontium-barium niobate pyroelectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-Curie-temperature strontium-barium niobate pyroelectric ceramic material and a preparation method thereof. The material has the composition general formula of SrxBa1-xNb2O6, wherein x is larger than or equal to 0.25 and smaller than or equal to 0.35. The SBN ceramic material high in density and pyroelectric performance is obtained by preparing power through a solid phase method, preparing an SBN blank through cold isostatic pressing forming and other processes, putting the SBN blank in a mold, filling and covering the SBN blank with ZrO2 powder, raising the temperature to 1100-1150 DEG C, linearly and evenly pressurizing to 100-200 MPa with the axis of the mold as the hot-press axis, raising the temperature to 1200-1300 DEG C, keeping the temperature and the pressure for 2-4 h in the air atmosphere, and linearly depressurizing and cooling inside a furnace to the room temperature. The problem that high-Curie-temperature SBN components are poor in pyroelectric performance is solved.
Description
Technical field
The invention belongs to infrared detecting materials field is and in particular to a kind of strontium barium niobate pyroelectric ceramic material and one kind are big
Width improves the preparation method of material pyroelectric property.
Background technology
Thermoelectric type Uncooled infrared detection technology have need not freeze, response spectrum width, fast response time, low cost etc.
Feature, becomes one of the most noticeable technology in current infrared detection technique.There is the ferroelectric ceramics of pyroelectric property (also referred to as
Make pyroelectric ceramics) it is one of crucial sensitive unit material of non-brake method infrared detection technique, its mode of operation can be divided into intrinsic heat
Release power mode and dielectric-pyroelectricity pattern.Intrinsic pyroelectricity pattern mainly utilizes spontaneous polarization variation with temperature, due to Curie
Temperature (tc) higher, near room temperature temperature stability is very good, without temperature stabilization device, in practical unit, polynary infrared
It is applied widely in detector.When ceramic material is applied to intrinsic pyroelectricity pattern Infrared Detectorss it is desirable to material
Pyroelectric coefficient is big, and dielectric constant, dielectric loss are relatively low, tcHigher.At present, as the ceramic material of intrinsic pyroelectricity pattern work
Material generally is perovskite structure system containing pb, such as lead zirconate titanate (pzt), the lead titanates (pct) mixing ca, lead magnesio-niobate-metatitanic acid
Lead (pmn-pt) etc., this is unfavorable for environmental conservation and human health, the grinding of unleaded pyroelectric ceramic material and its device
Studying carefully with exploitation is a urgent and significant problem.
sbn(srxbal-xnb206, 0.25≤x≤0.75) and pottery is SrNb2 O6 srnb2o6With niobic acid barium banb2o6Diploid
Tungsten bronze type solid solution in system.In sbn structure cell, nb is located at the inside b position of oxygen octahedra；sr2+And ba2+It is distributed in
Interstitial site al and a2.Due to 6 al and a2 positions a total of in sbn structure cell, and sr and ba atom only has 5, random distribution
On 6 a positions, so sbn belongs to non-fills up type tungsten bronze structure.This unfilled Multiple level special construction is to change material
Component and adjust its performance provide multiple probabilities.
However, the pyroelectric of the high-curie temperature sbn component pottery being obtained according to conventional sintering method is not good, how to draw
Enter suitable dopant ion or select suitable sintering process, have high t concurrently to obtaincSbn pottery with excellent pyroelectric property
Porcelain, makes sbn pottery meet the application requirement of thermoelectric type non-refrigerated infrared detector, and this is that those skilled in the art urgently solve
Technical problem certainly.According to literature survey result, the excellent general sr content of sbn pottery of pyroelectric property is higher, Curie temperature
tcRelatively low, depolarization occurs in actual Ceramic manufacturing with during using.As sr0.5ba0.5nb2o6Pyroelectricity under ceramic room temperature
Coefficient can reach 2.05 × 10-8c/cm2K, pyroelectricity figure of merit is respectively fi=0.976 × 10-10M/v, fv=1.136 ×
10-2m2/ c, fd=0.533 × 10-5pa-1/2, but its Curie temperature tcOnly 84 DEG C (j.zhang, g.s.wang, f.gao,
c.l.mao,f.cao,and x.l.dong,ceramics international.39(2),1971(2013).).It is actually used in
The pottery that rpyroelectric infrared detects needs higher tc, then the content of sr should be relatively low, sr0.3ba0.7nb2o6The Curie temperature t of potteryc
Up to 175 DEG C, but the pyroelectric coefficient under its room temperature is only 0.01 × 10-8c/cm2k(nishiwaki.s,takahashi.j,
and kodaira.k,journal of the ceramic society of japan.103(12),1246(1995)).
Content of the invention
It is contemplated that overcoming the not good technical problem of existing high-curie temperature sbn ferroelectric ceramics pyroelectric property, provide
A kind of preparation method that sbn pyroelectric ceramic material pyroelectric property is greatly improved, prepares one kind and has high t concurrentlycWith excellent
The sbn pottery of pyroelectric property, to substitute plumbum-based material, reaches the purpose of environmental protection.
On the one hand, the invention provides a kind of preparation method of high-curie temperature strontium barium niobate pyroelectric ceramic material, institute
The composition formula stating strontium barium niobate pyroelectric ceramic material is srxba1-xnb2o6, wherein 0.25≤x≤0.35；
Preparation method includes:
(1) stoichiometrically weigh raw material srco3Powder body, baco3Powder body and nb2o5Powder body, after a ball milling (wet ball-milling)
Calcine 2～4 hours at 1150～1230 DEG C, obtain sbn solid-solution powder；
(2) gained sbn solid-solution powder secondary ball milling (second wet ball-milling) is added afterwards binding agent, aged, sieve, cold
After isostatic pressing, plastic removal, obtain sbn base substrate；
(3) gained sbn base substrate is positioned in mould, using zro2 powder body, sbn base substrate is filled with and covers, be first warming up to
After 1100～1150 DEG C, then it is forced into 100～200mpa with the axis of mould for hot pressing direction of principal axis linear homogeneous and rises simultaneously
Temperature to 1200～1300 DEG C, heat-insulation pressure keeping 2～4 hours under air atmosphere, finally linear release furnace cooling cool to room temperature, obtain
To described sbn pyroelectric ceramic material.
With respect to other thermoelectric types sensitive unit material, sbn ceramic material is not leaded, and dielectric constant is moderate, dielectric loss
Relatively low, it is unleaded pyroelectric ceramic material and its important candidate material of devices field.In sbn, can be using change sr/ba
Ratio is adjusting Curie temperature tcConsecutive variations between 60～250 DEG C.The sbn ceramic material of the present invention is with solid phase method preparation
The techniques such as powder, cold isostatic compaction are obtained sbn base substrate；Sbn base substrate is positioned in graphite jig, with zro2Powder is filled in base
Around body and cover all base substrate, in air atmosphere along hot pressing direction of principal axis pressure sintering, that is, described sbn pyroelectricity pottery is obtained
Ceramic material.Sbn pyroelectric ceramics crystal grain using the method preparation is finer and close, and pyroelectric coefficient is increased dramatically, Ju Liwen
Degree is higher, and its sintering temperature is reduced to 1200～1300 DEG C simultaneously, is expected to be applied in non-refrigeration infrared detector.
It is preferred that the ball-milling medium of a described ball milling or/and secondary ball milling is in steel ball, zirconium ball or agate ball
Kind, solvent is dehydrated alcohol.
Also, it is preferred that the mass ratio=1:(1.5 of described raw material or sbn solid-solution powder and ball-milling medium and dehydrated alcohol
～2.0): (0.6～1.0).
It is preferred that plastic removal described in step (2) is to be incubated 1.5～2.5 hours at 750～850 DEG C.
It is preferred that the speed heating up described in step (3) is 1～3 DEG C/min, the speed of described linear release is 5～
10mpa/ minute.
On the other hand, present invention also offers a kind of high-curie temperature strontium barium niobate pyroelectric ceramic material, its feature exists
In, 160 DEG C of the Curie temperature ＞ of described strontium barium niobate pyroelectric ceramic material, and pyroelectric property is in the side perpendicular to hot pressing axle
To and parallel to the direction of hot pressing axle, there is anisotropy.
It is preferred that described strontium barium niobate pyroelectric ceramic material is 0.7 perpendicular to the axial pyroelectric coefficient of hot pressing
～1.3 × 10-8c/cm2K, pyroelectricity current-responsive figure of merit are 0.3～0.7 × 10-10M/v, voltage response figure of merit are
0.6～1.2 × 10-2m2/ c, the detectivity figure-of-merits factor are 0.2～0.5 × 10-5pa-1/2；
Described strontium barium niobate pyroelectric ceramic material is 1.2～2.6 × 10 parallel to the axial pyroelectric coefficient of hot pressing- 8c/cm2K, pyroelectricity current-responsive figure of merit are 0.5～1.3 × 10-10M/v, voltage response figure of merit be 1.2～2.1 ×
10-2m2/ c, the detectivity figure-of-merits factor are 0.4～0.8 × 10-5pa-1/2.
The present invention provides a kind of preparation side increasing substantially material pyroelectric property for sbn pyroelectric ceramic material
Method, by hot pressed sintering under air atmosphere, reduces the sintering temperature of sample, obtains the sbn heat of high-compactness, high pyroelectric property
Release electroceramics, solve the problems, such as that high-curie temperature sbn component pyroelectric property is poor.The sbn being obtained using the method for the present invention
Pyroelectric ceramics dielectric constant is moderate, Curie temperature height (160 DEG C of ＞), and pyroelectric coefficient improves 24%～235%, in pressurization
During 200mpa, the pyroelectric coefficient parallel to hot pressing direction of principal axis sample has reached 2.38 × 10-8c/cm2k.
Brief description
In Fig. 1, (a) and (b) is respectively the prepared sbn pyroelectric ceramics of embodiment 1 perpendicular to hot pressing axle and parallel to hot pressing
The stereoscan photograph of direction of principal axis sample, (c) and (d) is respectively the prepared sbn pyroelectric ceramics of embodiment 2 perpendicular to hot pressing axle
And the stereoscan photograph parallel to hot pressing direction of principal axis sample；
Fig. 2 is to release electroceramics its heat after polarization using the sbn being obtained in Quasi-static Method testing example 1 and embodiment 2
Release electrostrictive coefficient variation with temperature curve chart.
Specific embodiment
Further illustrate the present invention below by way of following embodiments it should be appreciated that following embodiment is merely to illustrate this
Invention, and the unrestricted present invention.
The present invention is with srco3Powder body, baco3Powder body and nb2o5Powder body is prepared for sbn pyroelectric ceramic material for raw material, its
Composition formula srxba1-xnb2o6, abbreviation sbn, wherein x are 0.25～0.35.The niobium that the explanation present invention in following exemplary ground provides
The preparation method of sour strontium barium pyroelectric ceramic material.
According to composition formula srxba1-xnb2o6(x is 0.25～0.35) weighs the srco of stoichiometric proportion3Powder body, baco3
Powder body and nb2o5Powder body, using the mixing of wet ball-milling method.Using wet ball-milling method to srco3Powder body, baco3Powder body and nb2o5
Powder body carries out in mixed process, one of the optional steel ball of ball-milling medium, zirconium ball or agate ball, and solvent is dehydrated alcohol.And institute
The mass ratio stating ball milling material, ball-milling medium and dehydrated alcohol can be 1:(1.0～1.5): (0.6～1.2), Ball-milling Time can be 12
～24 hours.
Then mixed powder is obtained sbn solid-solution powder through briquetting insulation synthesis.Close being incubated through briquetting by sbn powder body
During becoming preparation sbn solid solution, the temperature of described insulation synthesis is 1150～1230 DEG C.Temperature retention time is 2～4 hours.Close
After one-tenth, block is pulverized, cross 40 mesh sieves.
By sbn solid-solution powder pulverize after carry out secondary wet ball-milling, after drying add binding agent, aged, sieve, cold
The steps such as isostatic pressing, plastic removal are obtained sbn base substrate.Specifically, using wet ball-milling method by sbn solid-solution powder fine grinding 24
～48 hours.Wherein, ball milling material is sbn solid-solution powder, one of the optional steel ball of ball-milling medium, zirconium ball or agate ball.Molten
Agent is dehydrated alcohol.And ball milling material: ball-milling medium: dehydrated alcohol (mass ratio)=1:(1.5～2.0): (0.6～1.0)；Then
Dry powder, add certain density binding agent (pva) in right amount, aged, sieve, cold isostatic compaction, at 750～850 DEG C
Lower plastic removal 1.5～2.5 hours, obtains sbn base substrate.In above process, digestion time is 22～26 hours, crosses 40 mesh sieves.
Finally sbn base substrate is positioned in mould (such as graphite jig), with zro2Powder is filled in around base substrate and complete
Cover base substrate, start in air atmosphere along hot pressing axis pressure sintering, that is, described sbn pyroelectric ceramic material to be obtained.
The hot pressed sintering condition of described sbn base substrate is: sbn base substrate is positioned in graphite jig, uses zro2Powder is filled in
Around base substrate and cover all base substrate, rise to 1100～1150 DEG C with the programming rate of 1～3 DEG C/min, start with single shaft (heat
Last item) linear pressurization, continue with identical ramp to 1200～1300 DEG C simultaneously, when reaching maximum temperature point, pressure liter
To 100～200mpa, heat-insulation pressure keeping 2～4 hours.Finally room temperature is cooled to 5～10mpa/min linear release furnace cooling,
Whole sintering process is carried out in air atmosphere.
The sbn pyroelectric ceramic material being obtained after sintering is cut by parallel to hot pressing axle with perpendicular to hot pressing direction of principal axis respectively
Cut, be processed into required size, be cleaned by ultrasonic, silk screen printing silver paste, dry, be incubated 30 minutes at 700 DEG C～800 DEG C, obtain
Can be used for the sbn ceramics sample of electric property assessment.
160 DEG C of the Curie temperature ＞ of the strontium barium niobate pyroelectric ceramic material of present invention preparation, and pyroelectric property is vertical
There is anisotropy in the straight direction in hot pressing axle and the direction parallel to hot pressing axle.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential improvement that bright the above is made and adjustment belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only one of OK range example, and that is, those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Comparative example 1
Sr is prepared using conventional solid-state method0.3ba0.7nb2o6Powder body.It is first according to sr0.3ba0.7nb2o6Stoichiometric proportion weigh
srco3Powder body (analysis is pure), baco3Powder body (analysis is pure) and nb2o5Powder body (analysis is pure), adds and raw material gross weight identical
Dehydrated alcohol (analysis is pure), with agate ball as ball-milling medium, is mixed 24 hours using wet ball-milling method, makes each component mixing all
Even.Dry, add the deionized water of 5wt%, briquetting, 1200 DEG C of synthesis in air atmosphere, be incubated 3 hours, pulverize, cross 40 mesh
Sieve, obtains sr0.3ba0.7nb2o6Solid-solution powder.Again with wet ball-milling method fine grinding 48 hours, drying powder, addition 5wt% (with
Powder quality meter after drying) pva (concentration be 7wt%) binding agent, pelletize, be aged 24 hours, cross 40 mesh sieves, single shaft is suppressed
Molding, plastic removal at 800 DEG C, it is incubated 2 hours, that is, sr is obtained0.3ba0.7nb2o6Base substrate.Base substrate is sintered in atmosphere, with
The ramp of 2 DEG C/min to 1360 DEG C, is then incubated 4h, cools to room temperature with the furnace, obtain final product ordinary sinter pyroelectric ceramics material
Material sr0.3ba0.7nb2o6.
By two-sided for obtained pyroelectric ceramics sample mill, ultrasonic cleaning, dry, silk screen printing silver paste, then dry, 750
Silver ink firing 30min at DEG C, makes ceramics sample to measure its electric property.Gained ceramics sample is placed in silicone oil, is heated to 210
DEG C, then ceramics sample is applied with the DC electric field of 7kv/mm, carries out polarization process 60min, then keep the constant fall of electric field intensity
Low temperature, to 40 DEG C, removes electric field and takes out ceramics sample, measures it to the sample after polarization and is not added with outer pyroelectric property off field.
Embodiment 1
The present embodiment is at 3 points with the difference of comparative example 1: 1. sr0.3ba0.7nb2o6Base substrate is pressed into through isostatic cool pressing
Type.2. the sr being obtained0.3ba0.7nb2o6Base substrate is positioned in graphite jig, with zro2Powder is filled in around base substrate and covers completely
Cover base substrate, rise to 1150 DEG C with the programming rate of 1.5 DEG C/min, start single shaft and linearly pressurize, continue with same ramp
To 1260 DEG C, pressure reaches 100mpa, heat-insulation pressure keeping 4 hours simultaneously, is finally lowered the temperature with 10mpa/min linear release furnace cooling
To room temperature, whole sintering process is carried out in air atmosphere.3. by the sample sintering respectively by parallel to hot pressing axle and vertical
In the cutting of hot pressing direction of principal axis, cleaning, dry, silk screen printing silver paste, then dry, silver ink firing, carry out polarization process and electric property is surveyed
Examination.Remaining content of the present embodiment is all identical with described in comparative example 1.
By obtained pyroelectric ceramics thickness of sample be thinned to 0.5mm, successively using gasoline, liquid detergent, dehydrated alcohol, go
Ionized water is cleaned by ultrasonic 15 minutes respectively, uses silk screen printing silver paste after drying, sinters 30 minutes, make Ceramic Like at 750 DEG C
Product are to measure its electric property.The polarization process condition of ceramics sample is: gained ceramics sample is placed in silicone oil, heats silicone oil
To the DC electric field that when 210 DEG C, ceramics sample is applied with 7kv/mm, it is incubated 60min under 7kv/mm electric field, then keeps electric-field strength
Spend constant natural cooling and be cooled to 40 DEG C, remove electric field and take out ceramics sample.Finally it is measured not to the ceramics sample after polarization
Intrinsic pyroelectric property under Electric Field Biased.
Embodiment 2
The present embodiment the difference is that only, maximum pressure adds to 200mpa with embodiment 1.Remaining content of the present embodiment is equal
Identical with described in embodiment 1.
By obtained pyroelectric ceramics thickness of sample be thinned to 0.5mm, successively using gasoline, liquid detergent, dehydrated alcohol, go
Ionized water is cleaned by ultrasonic 15 minutes respectively, uses silk screen printing silver paste after drying, sinters 30 minutes, make Ceramic Like at 750 DEG C
Product are to measure its electric property.The polarization process condition of ceramics sample is: gained ceramics sample is placed in silicone oil, heats silicone oil
To the DC electric field that when 210 DEG C, ceramics sample is applied with 7kv/mm, it is incubated 60min under 7kv/mm electric field, then keeps electric-field strength
Spend constant natural cooling and be cooled to 40 DEG C, remove electric field and take out ceramics sample.Finally it is measured not to the ceramics sample after polarization
Intrinsic pyroelectric property under Electric Field Biased.
In Fig. 1, (a) (b) is respectively the prepared sbn pyroelectric ceramics of embodiment 1 perpendicular to hot pressing axle (⊥) and parallel to heat
The stereoscan photograph in last item (∥) direction；C () and (d) is respectively the prepared sbn pyroelectric ceramics of embodiment 2 perpendicular to hot pressing
Axle (⊥) and the stereoscan photograph parallel to hot pressing axle (∥) direction, crystal grain is finer and close, and average grain size is about 2 μm.
Fig. 2 is through polarization using the sbn pyroelectric ceramics being obtained in Quasi-static Method testing example 1 and embodiment 2
Afterwards, its pyroelectric coefficient variation with temperature curve chart.Temperature range is 20 DEG C～100 DEG C, and heating rate is 2 DEG C/min.By
In figure is visible, and with the increase of hot pressed sintering pressure, pyroelectric property is increased dramatically.
Table 1 is pyroelectric ceramic material (～25 DEG C) tests at room temperature obtained by comparative example 1 and embodiment 1 and 2
Electric property data.From in table, the sbn pyroelectric ceramics dielectric constant being obtained using hot-press method and dielectric loss are relatively
Low, Curie temperature is higher, and pyroelectric coefficient improves 24%～235%, when pressurizeing 200mpa, parallel to hot pressing axle (∥) side
Reach 2.38 × 10 to the pyroelectric coefficient of sample-8c/cm2K, pyroelectricity figure of merit is respectively fi=1.13 × 10-10m/
V, fv=1.89 × 10-2m2/ c, fd=0.63 × 10-5pa-1/2.
Table 1
Claims (9)
1. a kind of preparation method of high-curie temperature strontium barium niobate pyroelectric ceramic material is it is characterised in that described strontium barium niobate
The composition formula of pyroelectric ceramic material is srxba1-xnb2o6, wherein 0.25≤x≤0.35；
Preparation method includes:
(1) stoichiometrically weigh raw material srco3Powder body, baco3Powder body and nb2o5Powder body, after a ball milling 1150～
Calcine 2～4 hours at 1230 DEG C, obtain sbn solid-solution powder；
(2) will after gained sbn solid-solution powder secondary ball milling add binding agent, aged, sieve, cold isostatic compaction, plastic removal
Afterwards, obtain sbn base substrate；
(3) gained sbn base substrate is positioned in mould, using zro2Powder body is filled with to sbn base substrate and covers, and is first warming up to
After 1100～1150 DEG C, then it is forced into 100～200mpa with the axis of mould for hot pressing direction of principal axis linear homogeneous and rises simultaneously
Temperature to 1200～1300 DEG C, heat-insulation pressure keeping 2～4 hours under air atmosphere, finally linear release furnace cooling cool to room temperature, obtain
To described sbn pyroelectric ceramic material.
2. preparation method according to claim 1 is it is characterised in that the ball milling of a described ball milling or/and secondary ball milling
Medium is one of steel ball, zirconium ball or agate ball, and solvent is dehydrated alcohol.
3. preparation method according to claim 2 is it is characterised in that described raw material or sbn solid-solution powder are situated between with ball milling
Matter and mass ratio=1:(1.5～2.0 of dehydrated alcohol): (0.6～1.0).
4. the preparation method according to any one of claim 1-3 is it is characterised in that binding agent described in step (2) is
At least one in polyvinyl alcohol, polyvinyl butyral resin, polrvinyl chloride.
5. preparation method according to claim 4 is it is characterised in that the quality of described binding agent is sbn solid-solution powder
4～8%.
6. the preparation method according to any one of claim 1-5 it is characterised in that plastic removal described in step (2) be
It is incubated 1.5～2.5 hours at 750～850 DEG C.
7. the preparation method according to any one of claim 1-6 it is characterised in that described in step (3) heat up speed
Rate is 1～3 DEG C/min, and the speed of described linear release is 5～10mpa/ minute.
8. a kind of high-curie temperature strontium barium niobate pyroelectric ceramics material of the method preparation as any one of claim 1-7
Material is it is characterised in that 160 DEG C of the Curie temperature ＞ of described strontium barium niobate pyroelectric ceramic material, and its pyroelectric property is hanging down
The straight direction in hot pressing axle and the direction parallel to hot pressing axle have anisotropy.
9. high-curie temperature strontium barium niobate pyroelectric ceramic material according to claim 8 is it is characterised in that described niobic acid
Strontium barium pyroelectric ceramic material is 0.7～1.3 × 10 perpendicular to the axial pyroelectric coefficient of hot pressing-8c/cm2K, pyroelectricity
Current-responsive figure of merit is 0.3～0.7 × 10-10M/v, voltage response figure of merit are 0.6～1.2 × 10-2m2/ c, detection
Rate figure of merit is 0.2～0.5 × 10-5pa-1/2；
Described strontium barium niobate pyroelectric ceramic material is 1.2～2.6 × 10 parallel to the axial pyroelectric coefficient of hot pressing-8c/
cm2K, pyroelectricity current-responsive figure of merit are 0.5～1.3 × 10-10M/v, voltage response figure of merit are 1.2～2.1 × 10-2m2/ c, the detectivity figure-of-merits factor are 0.4～0.8 × 10-5pa-1/2.
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| CN114605151A (en) * | 2022-04-24 | 2022-06-10 | 西安理工大学 | Gd-Ta co-doped tungsten bronze structure ferroelectric energy storage ceramic material and preparation method thereof |
| CN114605151B (en) * | 2022-04-24 | 2022-12-09 | 西安理工大学 | Gd-Ta co-doped tungsten bronze structure ferroelectric energy storage ceramic material and preparation method thereof |
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Application publication date: 20170201 |