CN105753471A - Method for preparing strontium barium niobate ceramics with high pyroelectric effects - Google Patents
Method for preparing strontium barium niobate ceramics with high pyroelectric effects Download PDFInfo
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Abstract
The invention discloses a method for preparing strontium barium niobate ceramics with high pyroelectric effects.The method includes mixing raw materials BaCO<3>, SrCO<3> and Nb<2>O<5> according to a chemical formula of Sr<x>Ba<1-x>Nb<2>O<6> to obtain Sr<x>Ba<1-x>Nb<2>O<6> powder; sintering the Sr<x>Ba<1-x>Nb<2>O<6> powder by the aid of a spark plasma sintering system in a vacuum environment at the temperature of 1000-1050 DEG C to prepare ceramic sintered bodies and thermally treating the ceramic sintered bodies in the air at the temperature of 965-980 DEG C for 3 hours to obtain the strontium barium niobate ceramics with the high pyroelectric effects.The x can be equal to 0.4 or 0.5 or 0.6.The method has the advantages that the strontium barium niobate ceramics with the high pyroelectric effects have small crystal grain sizes and are high in density, the dielectric breakdown field strength is improved, accordingly, the strontium barium niobate ceramics hopefully can be used for solid-state refrigerating systems, and various currently confronted climatic environmental problems due to the fact that ozone layers are destructed by Freon which is used as a refrigerants can be solved.
Description
Technical field
The present invention relates to high electricity card effect ceramic material of solid-state electricity card refrigeration and energy collecting device and preparation method thereof.
Background technology
Electricity card effect (Electrocaloric Effect, hereinafter referred to as ECE) refers under adiabatic conditions, to material
When applying and remove electric field, material can produce the phenomenon of reversible temperature change, and it can effectively realize solid-state refrigeration components and parts
Efficiency.Can realize without greenhouse gas emission, the environmental disruption problem brought by cold-producing medium by solving freon provides one
Effective way.There is the material of relatively forceful electric power card effect at present and mainly have a following four classes: one, lead base composite perofskite；Two,
SrBi2Ta2O9Film；Three, BaTiO3、SrTiO3、Ba(1-x)SrxTiO3Class；Four, (vinylidene fluoride one trifluoro-ethylene) is base
Film.Above-mentioned leaded, secret compound electricity card effect is of a relatively high, but does not meets eco-friendly requirement, strontium titanates, metatitanic acid
The electric card effect of barium system is relatively weak, although organic polymer has a stronger electric card effect, but its poor heat stability.
These shortcomings limit their actual application, therefore there is presently no the electric card effect finding to meet actual operation requirements
Material.The existing research for electricity card effect material focuses primarily upon film, compares because film has for block
High electric card effect.The breakdown strength of ceramic block compares relatively low (the highest bear voltage≤100KV/cm), and film is permissible
Plus the highest electric field (～100-2000KV/cm).Although film single loop temperature declines relatively big in actual applications, by
In volume little, but its total thermal capacity is little.The volume ratio of ceramic block is bigger, although single loop temperature declines little, but
Being that its total thermal capacity is big, if so the electric calorific power of bi-material is more or less the same, the using value of block materials can be higher than thin
Membrane material.It addition, the preparation method of pottery can affect its micro-structural, and the performance micro-structural of pottery is relevant.
The compound of tungsten bronze structure is to be only second to the dielectric substance that a class of perovskite structure compound is important.Tungsten is blue or green
In the relaxation ferroelectric of steel structure, (formula is Sr to strontium barium niobatexBa1-xNb2O6, solution range 0.32≤x≤0.82, it is abbreviated as
SBN), because having pyroelectric effect, high photoelectric coefficient and the piezoelectric modulus of excellence, the most domestic and international research group is studied
Focus.
The strontium barium niobate ceramics of the heterogeneity that present invention discharge plasma sintering is prepared for.Have studied pottery in difference
At a temperature of polarization value, find that different sintering methods can affect the ferroelectric properties of pottery, thus affect ferroelectric effect.
Summary of the invention
Present invention aims to the deficiencies in the prior art, improve the system of a kind of high electricity card effect strontium barium niobate ceramics
Preparation Method, utilizes the maximum electric card effect of strontium barium niobate ceramics prepared by the method up to 0.51 DEG C.
It is an object of the invention to be achieved through the following technical solutions: the system of a kind of high electricity card effect strontium barium niobate ceramics
Preparation Method, comprises the following steps:
(1) by raw material BaCO3, SrCO3And Nb2O5By SrxBa1-xNb2O6Chemical formula dispensing, wherein x=0.4,0.5 or
0.6, being ground to particle diameter is 100nm～400nm post-drying, sieves；
(2) after the powder 1200 DEG C～1300 DEG C that step (1) prepares being calcined 3 hours, sieve, prepare SrxBa1-xNb2O6
Powder；
(3) Sr that step (2) is preparedxBa1-xNb2O6Powder loads the graphite jig of 10mm, utilizes plasma discharging to burn
Clone system 1000 DEG C～1050 DEG C sintering under vacuum conditions, prepare ceramic sintered bodies；
(4), under air atmosphere, the ceramic sintered bodies 960 DEG C～1000 DEG C step (3) prepared is heat-treated 3 hours, prepares
Described high electricity card strontium barium niobate ceramics.
Further, in described step (2), during x=0.4 or 0.5, calcine 3 hours for 1200 DEG C；During x=0.6,1300 DEG C
Calcine 3 hours.
Further, in described step (3), 1000 DEG C of sintering during x=0.4,1025 DEG C of sintering during x=0.5, during x=0.6
1050 DEG C of sintering.
Further, in described step (4), 980 DEG C of heat treatment during x=0.4,970 DEG C of heat treatment, x=0.6 during x=0.5
Time 965 DEG C of heat treatments.
Further, in step (1), the method for grinding is: raw material is put into ball grinder, adds zirconia ball and anhydrous second
Alcohol carries out ball milling.
The present invention is by using discharge plasma sintering method, and crystallite dimension is little and uniform, improves consistency and SrNb2 O6
The dielectric breakdown strength of titanate ceramics, thus improve the electric card effect of strontium barium niobate ceramics.
Before preparation, raw material needs to be ground to certain fineness, during grinding, raw material can be put into ball grinder, add oxidation
Zirconium ball and absolute ethyl alcohol carry out ball milling.
The beneficial effects of the present invention is: use the preparation method of the present invention, prepared SrxBa1-xNb2O6Pottery is in room temperature
Lower dielectric breakdown field intensity reaches 120kV/cm, and uses Sr prepared by conventional solid-state sintering methodxBa1-xNb2O6The dielectric of pottery
Disruptive field intensity is only 50kV/cm, and dielectric breakdown field intensity improves more than 2 times；Now, discharge plasma sintering temperature is 1000
DEG C, and use Sr prepared by conventional solid-state method methodxBa1-xNb2O6Ceramic sintering temperature is 1350 DEG C, and sintering temperature reduces
More than 300 DEG C；The electric calorific power of optimum strontium barium niobate ceramics prepared is 0.51 DEG C, and use prepared by conventional solid-state method method same
The electric calorific power of the strontium barium niobate ceramics of composition is only about 0.15 DEG C, and electricity card effect improves more than 3 times.Height prepared by the present invention
Electricity card strontium barium niobate ceramics, can be used for the components and parts such as solid-state refrigeration, it is not necessary to air compressor, volume can be made less,
Can be the refrigeration such as small-sized electronic product such as CPU, and in hgher efficiency, it is important to environmental protection, energy-conservation, efficient, stable and be prone to little
Type.Reducing under greenhouse effects and energy-intensive overall background the most urgent, electricity blocking cold-working is the refrigeration skill of green energy conservation
Art, becomes one of potential selection of people in the future, is highly desirable to it is strengthened research and development.
Accompanying drawing explanation
Fig. 1 is the XRD diffracting spectrum of strontium barium niobate ceramics sample: (a) Sr0.4Ba0.6Nb2O6(embodiment 1)；(b)
Sr0.5Ba0.5Nb2O6(embodiment 2)；(c)Sr0.6Ba0.4Nb2O6(embodiment 3)；D () conventional solid-state method prepares Sr0.6Ba0.4Nb2O6
(comparative example 1)；
Fig. 2 is the section SEM photograph of strontium barium niobate ceramics sample: (a) Sr0.4Ba0.6Nb2O6(embodiment 1)；(b)
Sr0.5Ba0.5Nb2O6(embodiment 2)；(c)Sr0.6Ba0.4Nb2O6(embodiment 3)；D () is prepared by conventional solid-state method
Sr0.6Ba0.4Nb2O6(comparative example 1)；
Fig. 3 be strontium barium niobate ceramics sample dielectric constant at different frequencies and dielectric loss variation with temperature bent
Line: (a), (b) Sr0.4Ba0.6Nb2O6(embodiment 1)；(c)、(d)Sr0.5Ba0.5Nb2O6(embodiment 2)；(e)、(f)
Sr0.6Ba0.4Nb2O6(embodiment 3)；
Fig. 4 is strontium barium niobate ceramics sample polarization changing value under different dielectric field intensity: (a) Sr0.4Ba0.6Nb2O6(real
Execute example 1)；(b)Sr0.5Ba0.5Nb2O6(embodiment 2)；(c)Sr0.6Ba0.4Nb2O6(embodiment 3)；
Fig. 5 is the strontium barium niobate ceramics sample electric calorific power under 10Hz and isothermal Entropy Changes value: (a), (b) Sr0.4Ba0.6Nb2O6
(embodiment 1)；(c)、(d)Sr0.5Ba0.5Nb2O6(embodiment 2)；；(e)、(f)Sr0.6Ba0.4Nb2O6(embodiment 3)；
Fig. 6 is the strontium barium niobate sample of tradition preparation electric calorific power under 10Hz and isothermal Entropy Changes value: (a), (b)
Sr0.6Ba0.4Nb2O6(comparative example 1).
Detailed description of the invention
The present invention is explained further below in conjunction with specific embodiment.
Embodiment 1
(1) by BaCO3, SrCO3And Nb2O5Material powder presses Sr respectively0.4Ba0.6Nb2O6Chemical formula weighs dispensing；
(2) chemical raw material that step (1) prepares is put into ball grinder, in baton round grinding jar and add ZrO2Zirconium ball, adds
Enter absolute ethyl alcohol, be placed on ball mill and carry out ball milling 24 hours (particle diameter is 100nm～400nm), the powder after ball milling is being dried
After drying in case, 120 mesh sieve.Prepared powder is calcined 3 hours at 1200 DEG C, after 2 DEG C/min cools to 1100 DEG C, with
Stove is cooled to room temperature, crosses 120 mesh sieves, prepares Sr0.4Ba0.6Nb2O6Powder；
(3) powder that step (2) prepares is loaded the graphite jig of a diameter of 10mm, puts into discharge plasma sintering system
Sinter under 1000 DEG C and 30MPa mechanical pressure, be incubated 5 minutes, be 100 DEG C/min from the heating rate of room temperature to 900 DEG C,
Being 40 DEG C/min from 900 DEG C to 980 DEG C heating rates, 980 DEG C to 1000 DEG C heating rates are 20 DEG C/min, 1000 DEG C of insulations
5min, after having sintered, sheds pressure and is cooled to 100 DEG C of taking-up samples with stove.
Discharge plasma sintering principle: discharge plasma sintering utilizes DC pulse current directly to carry out energising pressurization burning
Knot, controls heating rate by the watt level of regulation DC pulse current.Whole sintering process both can be under vacuum conditions
Carry out, also to carry out in protective atmosphere.Pulse current directly acts on sample and mould, fast heating, flash heat transfer, soon
Speed heats up, and significantly shortens sample sintering time.
(4) ceramics sample step (3) prepared is heat-treated 3 after grinding off the graphite paper of adhesion in atmosphere at 980 DEG C
Hour.It is 5 DEG C/min from the heating rate of room temperature to 980 DEG C, 980 DEG C of insulation 3h are cold with stove after having processed.And at air gas
Under atmosphere, it is heat-treated 3 hours at 980 DEG C and obtains having than Traditional preparation the pottery of high electricity card effect.
Embodiment 2
(1) by BaCO3, SrCO3And Nb2O5Material powder presses Sr respectively0.5Ba0.5Nb2O6Chemical formula weighs dispensing；
(2) chemical raw material that step (1) prepares is put into ball grinder, in baton round grinding jar and add ZrO2Zirconium ball, adds
Enter absolute ethyl alcohol, be placed on ball mill and carry out ball milling 24 hours (particle diameter is 100nm～400nm), the powder after ball milling is being dried
After drying in case, 120 mesh sieve.Prepared powder is calcined 3 hours at 1200 DEG C, after 2 DEG C/min cools to 1100 DEG C, with
Stove is cooled to room temperature, crosses 120 mesh sieves, prepares Sr0.5Ba0.5Nb2O6Powder；
(3) powder that step (2) prepares is loaded the graphite jig of a diameter of 10mm, puts into discharge plasma sintering system
Sinter under 1025 DEG C and 30MPa mechanical pressure, be incubated 5 minutes, be 100 DEG C/min from the heating rate of room temperature to 925 DEG C,
Being 40 DEG C/min from 925 DEG C to 1005 DEG C heating rates, 1005 DEG C to 1025 DEG C heating rates are 20 DEG C/min, 1025 DEG C of insulations
5min, after having sintered, sheds pressure and is cooled to 100 DEG C of taking-up samples with stove.
(4) ceramics sample step (3) prepared is heat-treated 3 after grinding off the graphite paper of adhesion in atmosphere at 980 DEG C
Hour.It is 5 DEG C/min from the heating rate of room temperature to 970 DEG C, 970 DEG C of insulation 3h are cold with stove after having processed.And at air gas
Under atmosphere, it is heat-treated 3 hours at 970 DEG C and obtains having than Traditional preparation the pottery of high electricity card effect.
Embodiment 3
(1) by BaCO3, SrCO3And Nb2O5Material powder presses Sr respectively0.6Ba0.4Nb2O6Chemical formula weighs dispensing；
(2) chemical raw material that step (1) prepares is put into ball grinder, in baton round grinding jar and add ZrO2Zirconium ball, adds
Enter absolute ethyl alcohol, be placed on ball mill and carry out ball milling 24 hours (particle diameter is 100nm～400nm), the powder after ball milling is being dried
After drying in case, 120 mesh sieve.Prepared powder is calcined 3 hours at 1300 DEG C, after 2 DEG C/min cools to 1100 DEG C, with
Stove is cooled to room temperature, crosses 120 mesh sieves, prepares Sr0.6Ba0.4Nb2O6Powder；
(3) powder that step (2) prepares is loaded the graphite jig of a diameter of 10mm, puts into discharge plasma sintering system
Sinter under 1050 DEG C and 30MPa mechanical pressure, be incubated 5 minutes, be 100 DEG C/min from the heating rate of room temperature to 950 DEG C,
Being 40 DEG C/min from 950 DEG C to 1030 DEG C heating rates, 1030 DEG C to 1050 DEG C heating rates are 20 DEG C/min, 1050 DEG C of insulations
5min, after having sintered, sheds pressure and is cooled to 100 DEG C of taking-up samples with stove.
(4) ceramics sample step (3) prepared is heat-treated 3 after grinding off the graphite paper of adhesion in atmosphere at 965 DEG C
Hour.It is 5 DEG C/min from the heating rate of room temperature to 965 DEG C, 965 DEG C of insulation 3h are cold with stove after having processed.And at air gas
Under atmosphere, it is heat-treated 3 hours at 960 DEG C and obtains having than Traditional preparation the pottery of high electricity card effect.
Comparative example 1
Sr is provided0.6Ba0.4Nb2O6The conventional solid-state method preparation process of pottery:
(1) by BaCO3, SrCO3And Nb2O5Material powder presses Sr respectively0.6Ba0.4Nb2O6Chemical formula weighs dispensing；
(2) chemical raw material that step (1) prepares is put into ball grinder, in baton round grinding jar and add ZrO2Zirconium ball, adds
Enter absolute ethyl alcohol, be placed on ball mill and carry out ball milling 24 hours (particle diameter is 100nm～400nm), the powder after ball milling is being dried
After drying in case, 120 mesh sieve.Prepared powder is calcined 3 hours at 1300 DEG C, after 2 DEG C/min cools to 1100 DEG C, with
Stove is cooled to room temperature, crosses 120 mesh sieves, prepares Sr0.6Ba0.4Nb2O6Powder；
(3) powder that step (2) prepares being added 8wt% concentration is that the polyvinyl alcohol (PVA) of 5vol% is as binding agent
After grinding granulation, cross 40 mesh sieves, it is therefore an objective to increase mobility and the plasticity of powder.Then make under the single-phase pressure of 98MPa
Become the cylindrical idiosome of a diameter of 12mm, thickness about 2mm.
(4) idiosome that step (3) prepares is put into 600 DEG C of plastic removal 2h of alumina crucible, in order to prevent idiosome and earthenware
Crucible reacts, and powder identical with idiosome on alumina crucible lid is more higher bedding and padding than sintering temperature, then in air atmosphere
1350 DEG C sinter 3 hours, after 2 DEG C/min drops to 1100 DEG C, cool down with stove, obtain Sr0.6Ba0.4Nb2O6Pottery.
By embodiment 1～3 and the cylindrical dielectric ceramics sample abrasive paper for metallograph for preparing of comparative example 1 and polishing machine
Sanding and polishing to thickness is about 0.5mm, and then the upper and lower surface at sample deposits gold thin film as electrode with sputter.Utilize
The ferroelectric hysteresis loop at lower 0 DEG C to 165 DEG C of its 10Hz frequency measured by ferroelectricity analyzer, utilizes indirect method to calculate its electricity card effect.
Table 1
From fig. 1, it can be seen that ceramic sample prepared by two kinds of sintering process is all single-phase.As shown in Figure 2, discharge plasma sintering
It is little that the relatively conventional solid phase method of crystal grain of the strontium barium niobate ceramics of preparation sinters, and consistency is high.As can be seen from Figure 3, Jie of sample
Electric constant reduces along with the increase of x, and the temperature in phase transformation curie point is TC, at TCPlace, the dielectric constant of sample is maximum,
Curie temperature TCReduce also with the increase of x, Sr0.6Ba0.4Nb2O6The Curie temperature of pottery is close to room temperature.As shown in Figure 4, with
The rising of temperature, the polarization value of strontium barium niobate ceramics reduces, and reduces fastest near Curie point.By Fig. 5,6 can
Knowing, the disruptive field intensity of strontium barium niobate ceramics prepared by plasma discharging and electricity calorific power significantly improve.Prepare compared to conventional solid
Pottery prepared by method, disruptive field intensity increases to 80kV/cm from 50kV/cm.Therefore its electricity calorific power improves, the most accordingly at x=0.6
Time, Sr0.6Ba0.4Nb2O6The electric calorific power of pottery reaches maximum 0.51 DEG C, improves more than 3 times than prepared by conventional solid-state method.
Table 1 shows the Sr utilizing the preparation method of the present invention to preparexBa1-xNb2O6Pottery and utilize conventional solid-state method
Sr prepared by sintering method0.6Ba0.4Nb2O6Pottery is 0 DEG C to 165 DEG C in temperature, the dielectric breakdown strength under 10Hz frequency and electricity
Calorific power, as shown in Table 1, the Sr that the present invention preparesxBa1-xNb2O6The highest electricity calorific power of pottery is 0.51 DEG C, and utilizes conventional solid
The Sr of identical component prepared by sintering method0.6Ba0.4Nb2O6The electric calorific power of pottery is only 0.15 DEG C.
Claims (5)
1. the preparation method of one kind high electricity card effect strontium barium niobate ceramics, it is characterised in that comprise the following steps:
(1) by raw material BaCO3, SrCO3And Nb2O5By SrxBa1-xNb2O6Chemical formula dispensing, wherein x=0.4,0.5 or 0.6, grind
It is 100nm～400nm post-drying to particle diameter, sieves；
(2) after the powder 1200 DEG C～1300 DEG C that step (1) prepares being calcined 3 hours, sieve, prepare SrxBa1-xNb2O6Powder；
(3) Sr that step (2) is preparedxBa1-xNb2O6Powder loads the graphite jig of 10mm, utilizes discharge plasma sintering system
System 1000 DEG C～1050 DEG C sintering under vacuum conditions, prepare ceramic sintered bodies；
(4) under air atmosphere, the ceramic sintered bodies 960 DEG C～1000 DEG C step (3) prepared is heat-treated 3 hours, prepares described
High electricity card strontium barium niobate ceramics.
2. preparation method as claimed in claim 1, it is characterised in that in described step (2), during x=0.4 or 0.5,1200 DEG C
Calcine 3 hours；During x=0.6, calcine 3 hours for 1300 DEG C.
3. preparation method as claimed in claim 1, it is characterised in that in described step (3), 1000 DEG C of sintering during x=0.4；x
1025 DEG C of sintering when=0.5；1050 DEG C of sintering during x=0.6.
4. preparation method as claimed in claim 1, it is characterised in that in described step (4), 980 DEG C of heat treatment during x=0.4；
970 DEG C of heat treatment during x=0.5；965 DEG C of heat treatment during x=0.6.
5. preparation method as claimed in claim 1, it is characterised in that in step (1), the method for grinding is: put into by raw material
Ball grinder, adds zirconia ball and absolute ethyl alcohol carries out ball milling.
Priority Applications (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106365636A (en) * | 2016-08-26 | 2017-02-01 | 中国科学院上海硅酸盐研究所 | High-Curie-temperature strontium-barium niobate pyroelectric ceramic material and preparation method thereof |
| CN106938929A (en) * | 2017-03-23 | 2017-07-11 | 同济大学 | The preparation method of the unleaded relaxation ferroelectric ceramic of the high electric card effect of room temperature |
| CN112062553A (en) * | 2020-09-17 | 2020-12-11 | 广西大学 | Negative electrocaloric effect Pb (Zr) of ultra-wide temperature zonexTi1-x)O3Method for producing base film |
| CN112979312A (en) * | 2021-04-30 | 2021-06-18 | 昆明理工大学 | AB2O6Niobate ceramic and preparation method thereof |
| CN116425537A (en) * | 2023-04-11 | 2023-07-14 | 西安理工大学 | Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material and preparation method thereof |
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| CN103011803A (en) * | 2012-12-11 | 2013-04-03 | 浙江大学 | Leadless ceramic with high thermoelectric effect and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106365636A (en) * | 2016-08-26 | 2017-02-01 | 中国科学院上海硅酸盐研究所 | High-Curie-temperature strontium-barium niobate pyroelectric ceramic material and preparation method thereof |
| CN106938929A (en) * | 2017-03-23 | 2017-07-11 | 同济大学 | The preparation method of the unleaded relaxation ferroelectric ceramic of the high electric card effect of room temperature |
| CN106938929B (en) * | 2017-03-23 | 2020-08-14 | 同济大学 | Method for preparing room temperature high electric card effect leadless relaxation ferroelectric ceramic |
| CN112062553A (en) * | 2020-09-17 | 2020-12-11 | 广西大学 | Negative electrocaloric effect Pb (Zr) of ultra-wide temperature zonexTi1-x)O3Method for producing base film |
| CN112062553B (en) * | 2020-09-17 | 2022-09-06 | 广西大学 | Negative electricity card effect Pb (Zr) of super wide temperature zone x Ti 1-x )O 3 Method for producing base film |
| CN112979312A (en) * | 2021-04-30 | 2021-06-18 | 昆明理工大学 | AB2O6Niobate ceramic and preparation method thereof |
| CN116425537A (en) * | 2023-04-11 | 2023-07-14 | 西安理工大学 | Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material and preparation method thereof |
| CN116425537B (en) * | 2023-04-11 | 2024-03-15 | 西安理工大学 | Zr-doped strontium barium gadolinium niobate-zirconium dioxide composite ceramic material and preparation method thereof |
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