CN102503410B - Preparation method of barium strontium titanate-lead titanate pyroelectric ceramic - Google Patents
Preparation method of barium strontium titanate-lead titanate pyroelectric ceramic Download PDFInfo
- Publication number
- CN102503410B CN102503410B CN 201110340843 CN201110340843A CN102503410B CN 102503410 B CN102503410 B CN 102503410B CN 201110340843 CN201110340843 CN 201110340843 CN 201110340843 A CN201110340843 A CN 201110340843A CN 102503410 B CN102503410 B CN 102503410B
- Authority
- CN
- China
- Prior art keywords
- titanate
- strontium
- lead
- barium titanate
- lead titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a barium strontium titanate-lead titanate pyroelectric ceramic and a preparation method thereof, the preparation method comprises the steps of: (1) dissolving lead nitrate, barium nitrate and strontium nitrate in deionized water according to a chemical formula proportion of (1-y)Ba1-xSrxTiO3-yPbTiO3, and adding citric acid with mol ratio to metal ions of 1:2 to prepare a mixed solution; dissolving butyl titanate in ethylene glycol to obtain a butyl titanate solution; blending and stirring the mixed solution with the butyl titanate solution, and regulating the pH value to obtain a precursor solution; and drying the precursor solution to gel; (2) calcining the gel in a muffle furnace to synthesize barium strontium titanate-lead titanate powder; (3) pressing the barium strontium titanate-lead titanate powder to a blank body, and sintering the blank body under the protection of lead atmosphere to prepare the barium strontium titanate-lead titanate pyroelectric ceramic. The preparation method of the invention has the advantages that a proper dosage of PT is doped on a BST ceramic base to prepare a composite ferroelectric ceramic relaxation material with better performance; and the method has the advantages of greatly reducing the synthesis temperature of the powder perovskite phase, reducing the dimensions of the powder granules for an order of magnitude, and guaranteeing the uniform distribution of the granules.
Description
Technical field
The present invention relates to a kind of pyroelectric ceramics, especially relate to the preparation method of a kind of strontium-barium titanate-lead titanate pyroelectric ceramics.
Background technology
Pyroelectric infrared sensor utilizes the pyroelectric effect of material to survey infrared energy, works at ambient temperature, and detection sensitivity is very high, and is irrelevant with radiation wavelength, and the pyroelectric electric device response is very fast, and it is convenient to use.Pyroelectric infrared sensor is one of at present most widely used transmitter, is applied to military affairs and industrial occasions such as remote sensing, guidance, night vision, active radar, thermal imaging, gasometry, radiometer, thermometric.The pyroelectric infrared sensor material can be divided into monocrystal material, stupalith and macromolecule membrane etc.The excellent performance of pyroelectric single crystal material but often preparation difficulty, cost are high, and compare with pyroelectric single crystal material, pyroelectric ceramics has series of advantages, as is easy to make large-area device, and the spontaneous polarization strength height can be produced in enormous quantities, and cost is low.In addition, in pottery, can carry out diversified doping and replacement, can in sizable scope, regulate its performance, as pyroelectric coefficient, specific inductivity and dielectric loss etc., thus further improve the performance of pyroelectricity material.
Pyroelectric ceramics is the core parts of pyroelectric infrared sensor, it is big that people wish to seek a kind of pyroelectric coefficient always, detection figure of merit height, thermal diffusivity is little, dielectric loss is little, and performance is uniform and stable, and processes easily and the novel pyroelectricity material of characteristics such as use, and traditional pyroelectricity material (PZT etc.) is difficult to satisfy simultaneously these actual application requiring, and this just makes explores the active demand that high performance novel pyroelectricity material becomes present development room temperature infrared sensor.
BaSrTiO
3(BST) be a kind of have good pyroelectric coefficient, high ferroelectric material of surveying the figure of merit, but because its Curie temperature is lower, and need be under quite high temperature could synthesis of densified, have the well behaved BST stupalith of perovskite structure, thereby limited the Application Areas of BST stupalith.And PbTiO
3(PT) lead titanate ceramics have good ferroelectric, piezoelectricity, dielectric, pyroelectricity and electro-optical characteristic.Therefore, mixing PT on the BST base makes two yuan of composite ceramicses and might obtain the better ferroelectric relaxation material of performance.By adjusting stoichiometric ratio, doping and material microstructure being controlled etc., in very wide scope, adjust the Curie temperature and the pyroelectric property of strontium-barium titanate-lead titanate ceramics material; Advantages such as it has the high pyroelectric coefficient of wide temperature range, surveys figure of merit height, and thermal diffusivity is little, and dielectric loss is little.The soft chemical method that adopts can reduce the synthesis temperature of powder uhligite phase, the little order of magnitude of the also more traditional solid phase synthesis process of resulting powder granule size, and size distribution is also very even.The open report that also is not used for pyroelectricity material so far about strontium-barium titanate-lead titanate ceramics.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of to have a pyroelectric coefficient big, surveys figure of merit height, and thermal diffusivity is little, the preparation method of the strontium-barium titanate that dielectric loss is little-lead titanate pyroelectric ceramics.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the preparation method of a kind of strontium-barium titanate-lead titanate pyroelectric ceramics may further comprise the steps:
(1) according to chemical formula (1-y) Ba
1-xSr
xTiO
3-yPbTiO
3, get x=0.2-0.5, y=0.1-0.25, chemical formula ratio weighing lead nitrate, nitrate of baryta and strontium nitrate in above-mentioned are dissolved in the deionized water at normal temperatures, add again with the metal ion mol ratio be that the citric acid of 1:2 obtains mixing solutions; Be dissolved in above-mentioned identical chemical formula ratio weighing butyl (tetra) titanate and obtain butyl (tetra) titanate solution in the ethylene glycol; Above-mentioned mixing solutions is mixed the back stir more than 1 hour with butyl (tetra) titanate solution, regulate its pH value to 7～9 with rare nitric acid then, obtain strontium-barium titanate-lead titanate precursor liquid; Strontium-barium titanate-lead titanate precursor liquid is put into baking oven, and oven dry was made strontium-barium titanate-lead titanate gel more than 30 hours under 130～150 ℃ of conditions;
(2) strontium-barium titanate that step (1) is obtained-lead titanate gel is put into retort furnace, at 450-600 ℃ temperature calcining 3～6 hours, synthetic strontium-barium titanate-lead titanate powder;
(3) strontium-barium titanate-lead titanate powder that step (2) is obtained is pressed into base substrate under 100-120MPa pressure, and base substrate is placed airtight double-deck corundum crucible, and adds PbOZrO between two crucibles
2Filler to be keeping plumbous atmosphere, and base substrate 850-950 ℃ of temperature sintering 2～4 hours, is made strontium-barium titanate-lead titanate pyroelectric ceramics.
Compared with prior art, the invention has the advantages that:
Mix an amount of PT on the BST ceramic base, available can better two yuan of ferroelectric relaxation materials of composite ceramics.Advantages such as it has the Curie temperature height, and the high pyroelectric coefficient of wide temperature range is surveyed figure of merit height, and thermal diffusivity is little, and dielectric loss is little.Compare with traditional pyroelectric ceramics, on some performance, obtained the strontium-barium titanate-lead titanate ceramics material of bigger raising, can satisfy different needs.On the other hand, strontium-barium titanate of the present invention-lead titanate ceramics preparation methods is simple, production cost is lower, have that chemical composition is regulated easily, the repeatability of technology and advantage such as controllability is strong, the stupalith sintering temperature is low, agglomerated material uniform component, density height and crystallization phases structure tend towards stability, the sample that makes has good physicals.
Description of drawings
Fig. 1 is the SEM figure of the 1st group of sample of specific embodiment;
Fig. 2 is the pyroelectric coefficient figure of the 1st, 2,3 groups of samples of specific embodiment.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
Strontium-barium titanate-lead titanate binary system ceramics (0.9Ba
0.65Sr
0.35TiO
3-0.1PbTiO
3) compositing formula is: Ba
0.65Sr
0.35TiO
3: 90atm%, PbTiO
3: 10atm%, the technology that the two component system primitive of above compositing formula prepares the single-component pyroelectric ceramic material is as follows:
(1) in above-mentioned chemical formula ratio weighing lead nitrate, nitrate of baryta and strontium nitrate, be dissolved at normal temperatures in the deionized water, add again with the metal ion mol ratio be that the citric acid of 1:2 obtains mixing solutions; Be dissolved in above-mentioned identical chemical formula ratio weighing butyl (tetra) titanate and obtain butyl (tetra) titanate solution in the ethylene glycol; Above-mentioned mixing solutions is mixed the back stirred 1 hour with butyl (tetra) titanate solution, regulate its pH value to 7～9 with rare nitric acid then, obtain strontium-barium titanate-lead titanate precursor liquid; Strontium-barium titanate-lead titanate precursor liquid is put into baking oven, and oven dry is 31 hours under 130 ℃ of conditions, makes strontium-barium titanate-lead titanate gel;
(2) strontium-barium titanate that step (1) is obtained-lead titanate gel is put into retort furnace, at 450 ℃ temperature calcinings 5 hours, synthetic strontium-barium titanate-lead titanate powder;
(3) strontium-barium titanate-lead titanate powder that step (2) is obtained is pressed into base substrate under 120MPa pressure, and base substrate is placed airtight double-deck corundum crucible, and adds PbOZrO between two crucibles
2Filler to be keeping plumbous atmosphere, and base substrate 900 ℃ of temperature sintering 2 hours, is made strontium-barium titanate-lead titanate pyroelectric ceramics.
(4) with the sample abrasive disc behind the sintering, cleaning, by silver, burn electrode, the 15-30min that then sample polarized in 100 ℃ silicone oil, polarizing voltage is 3-5kV/mm, leaves standstill test performance behind the 24h.
As can be seen from the figure, the material grains uniform particles, the structure unanimity, ceramic powder crystal grain is approximately 10～20 μ m.
Can find out pyroelectric coefficient along with the increase of PT content reduces to some extent from the Changing Pattern of pyroelectric coefficient data, and Mn ion doping pyroelectric coefficient increases.
85 ℃ of the Curie temperature of the 1st group of sample strontium-barium titanate of specific embodiment-lead titanate two component system pyroelectric ceramics, pyroelectric coefficient p=10.1 * 10
-4Cm
-2K
-1, relative permittivity ε
r=540, figure of merit F is surveyed in dielectric loss factor Tan δ=0.021
d=4.6 * 10
-5Pa
-1/2Curie temperature (0-30 ℃) than BST pyroelectric ceramics is high, and the strontium-barium titanate-lead titanate ceramics of preparation have high pyroelectric coefficient in wide temperature range, and its pyroelectric ceramic material over-all properties is better.In the pyroelectricity field great using value is arranged.
Strontium-barium titanate-pottery (the 0.8Ba of lead titanate system
0.55Sr
0.45TiO
3-0.2PbTiO
3) compositing formula is: Ba
0.55Sr
0.45TiO
3: 80atm%, PbTiO
3: 20atm%, the technology that the two component system primitive of above compositing formula prepares the single-component pyroelectric ceramic material is as follows:
(1) in above-mentioned chemical formula ratio weighing lead nitrate, nitrate of baryta and strontium nitrate, be dissolved at normal temperatures in the deionized water, add again with the metal ion mol ratio be that the citric acid of 1:2 obtains mixing solutions; Be dissolved in above-mentioned identical chemical formula ratio weighing butyl (tetra) titanate and obtain butyl (tetra) titanate solution in the ethylene glycol; Above-mentioned mixing solutions is mixed the back stirred 2 hours with butyl (tetra) titanate solution, regulate its pH value to 7～9 with rare nitric acid then, obtain strontium-barium titanate-lead titanate precursor liquid; Strontium-barium titanate-lead titanate precursor liquid is put into baking oven, and oven dry is 36 hours under 150 ℃ of conditions, makes strontium-barium titanate-lead titanate gel;
(2) strontium-barium titanate that step (1) is obtained-lead titanate gel is put into retort furnace, at 500 ℃ temperature calcinings 6 hours, synthetic strontium-barium titanate-lead titanate powder;
(3) strontium-barium titanate-lead titanate powder that step (2) is obtained is pressed into base substrate under 100MPa pressure, and base substrate is placed airtight double-deck corundum crucible, and adds PbOZrO between two crucibles
2Filler to be keeping plumbous atmosphere, and base substrate 850 ℃ of temperature sintering 3 hours, is made strontium-barium titanate-lead titanate pyroelectric ceramics.
(4) with the sample abrasive disc behind the sintering, cleaning, by silver, burn electrode, the 15-30min that then sample polarized in 100-120 ℃ silicone oil, polarizing voltage is 3-5kV/mm, leaves standstill test performance behind the 24h.
Curie temperature by the strontium-barium titanate-lead titanate two component system pyroelectric ceramics of above-mentioned prepared is 87 ℃, pyroelectric coefficient p=9.5 * 10
-4Cm
-2K
-1, relative permittivity ε
r=535, figure of merit F is surveyed in dielectric loss factor Tan δ=0.018
d=4.8 * 10
-5Pa
-1/2The pyroelectric coefficient of strontium-barium titanate-lead titanate system pottery is along with the increase of PT content reduces to some extent.
Mix Mn strontium-barium titanate-lead titanate (Mn-doped0.9Ba
0.5Sr
0.5TiO
3-0.1PbTiO
3) ceramic compositing formula is: Ba
0.5Sr
0.5TiO
3: 90atm%, PbTiO
3: 10atm%, mix Mn (NO outward
3)
2Volumetric molar concentration 2atm%.The technology that the two component system primitive of above compositing formula prepares the single-component pyroelectric ceramic material is as follows:
(1) in above-mentioned chemical formula ratio weighing lead nitrate, nitrate of baryta and strontium nitrate, be dissolved at normal temperatures in the deionized water, add again with the metal ion mol ratio be that the citric acid of 1:2 obtains mixing solutions; Be dissolved in above-mentioned identical chemical formula ratio weighing butyl (tetra) titanate and obtain butyl (tetra) titanate solution in the ethylene glycol; Above-mentioned mixing solutions is mixed the back stirred 1 hour with butyl (tetra) titanate solution, regulate its pH value to 7～9 with rare nitric acid then, obtain strontium-barium titanate-lead titanate precursor liquid; Strontium-barium titanate-lead titanate precursor liquid is put into baking oven, and oven dry is 40 hours under 140 ℃ of conditions, makes strontium-barium titanate-lead titanate gel;
(2) strontium-barium titanate that step (1) is obtained-lead titanate gel is put into retort furnace, at 600 ℃ temperature calcinings 6 hours, synthetic strontium-barium titanate-lead titanate powder;
(3) strontium-barium titanate-lead titanate powder that step (2) is obtained is pressed into base substrate under 110MPa pressure, and base substrate is placed airtight double-deck corundum crucible, and adds PbOZrO between two crucibles
2Filler to be keeping plumbous atmosphere, and base substrate 950 ℃ of temperature sintering 4 hours, is made strontium-barium titanate-lead titanate pyroelectric ceramics.
(4) with the sample abrasive disc behind the sintering, cleaning, by silver, burn electrode, the 15-30min that then sample polarized in 100-120 ℃ silicone oil, polarizing voltage is 3-5kV/mm, leaves standstill test performance behind the 24h.
Mix 90 ℃ of the Curie temperature that Mn strontium-barium titanate-lead titanate is a pyroelectric ceramics, pyroelectric coefficient p=12.2 * 10 by the 3rd group of sample of specific embodiment of above-mentioned prepared
-4Cm
-2K
-1, relative permittivity ε
r=530, figure of merit F is surveyed in dielectric loss factor Tan δ=0.023
d=5.3 * 10
-5Pa
-1/2Hence one can see that, mixes the pyroelectric coefficient maximum of Mn strontium-barium titanate-lead titanate, and over-all properties is optimum in an embodiment.
Claims (1)
1. the preparation method of strontium-barium titanate-lead titanate pyroelectric ceramics is characterized in that may further comprise the steps:
(1) according to chemical formula (1-y) Ba
1-xSr
xTiO
3-yPbTiO
3, get x=0.2-0.5, y=0.1-0.25, chemical formula ratio weighing lead nitrate, nitrate of baryta and strontium nitrate in above-mentioned are dissolved in the deionized water at normal temperatures, add again with the metal ion mol ratio be that the citric acid of 1:2 obtains mixing solutions; Be dissolved in above-mentioned identical chemical formula ratio weighing butyl (tetra) titanate and obtain butyl (tetra) titanate solution in the ethylene glycol; Above-mentioned mixing solutions is mixed the back stir more than 1 hour with butyl (tetra) titanate solution, regulate its pH value to 7～9 with rare nitric acid then, obtain strontium-barium titanate-lead titanate precursor liquid; Strontium-barium titanate-lead titanate precursor liquid is put into baking oven, and oven dry was made strontium-barium titanate-lead titanate gel more than 30 hours under 130～150 ℃ of conditions;
(2) strontium-barium titanate that step (1) is obtained-lead titanate gel is put into retort furnace, at 450-600 ℃ temperature calcining 3～6 hours, synthetic strontium-barium titanate-lead titanate powder;
(3) strontium-barium titanate-lead titanate powder that step (2) is obtained is pressed into base substrate under 100-120MPa pressure, and base substrate is placed airtight double-deck corundum crucible, and adds PbOZrO between two crucibles
2Filler to be keeping plumbous atmosphere, and base substrate 850-950 ℃ of temperature sintering 2～4 hours, is made strontium-barium titanate-lead titanate pyroelectric ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110340843 CN102503410B (en) | 2011-11-02 | 2011-11-02 | Preparation method of barium strontium titanate-lead titanate pyroelectric ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110340843 CN102503410B (en) | 2011-11-02 | 2011-11-02 | Preparation method of barium strontium titanate-lead titanate pyroelectric ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102503410A CN102503410A (en) | 2012-06-20 |
| CN102503410B true CN102503410B (en) | 2013-07-31 |
Family
ID=46215561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110340843 Expired - Fee Related CN102503410B (en) | 2011-11-02 | 2011-11-02 | Preparation method of barium strontium titanate-lead titanate pyroelectric ceramic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102503410B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496471A (en) * | 2014-11-26 | 2015-04-08 | 中国科学院上海硅酸盐研究所 | High-Curie-temperature lead-free pyroelectric ceramic material and preparation method thereof |
| CN108545771B (en) * | 2018-07-03 | 2020-06-16 | 电子科技大学 | Preparation method of barium strontium titanate aerogel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100376A (en) * | 2007-07-17 | 2008-01-09 | 上海师范大学 | Lead magnesio-niobate-lead titanate binary system high-heat electricity-release ceramic material and preparation technique thereof |
| CN101625268A (en) * | 2009-07-07 | 2010-01-13 | 华中科技大学 | Preparation method of porous field pyroelectric ceramic material |
-
2011
- 2011-11-02 CN CN 201110340843 patent/CN102503410B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100376A (en) * | 2007-07-17 | 2008-01-09 | 上海师范大学 | Lead magnesio-niobate-lead titanate binary system high-heat electricity-release ceramic material and preparation technique thereof |
| CN101625268A (en) * | 2009-07-07 | 2010-01-13 | 华中科技大学 | Preparation method of porous field pyroelectric ceramic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102503410A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Crystallization, phase evolution and ferroelectric properties of sol–gel-synthesized Ba (Ti 0.8 Zr 0.2) O 3–x (Ba 0.7 Ca 0.3) TiO 3 thin films | |
| Kalem et al. | Dielectric and piezoelectric properties of PMN-PT ceramics doped with strontium | |
| Zhang et al. | Low temperature preparation and electrical properties of sodium–potassium bismuth titanate lead-free piezoelectric thick films by screen printing | |
| CN109321979B (en) | Barium strontium titanate single crystal and preparation method thereof | |
| CN102910902A (en) | BNT-BT-BKT-based perovskite system multielement lead-free piezoelectric ceramic and production method thereof | |
| Huang et al. | Structural phase transition, electrical and photoluminescent properties of Pr3+-doped (1-x) Na0. 5Bi0. 5TiO3-xSrTiO3 lead-free ferroelectric thin films | |
| Tian et al. | Diversiform electrical and thermal expansion properties of (1− x) Ba0. 95Ca0. 05Ti0. 94Zr0. 06O3–(x) Dy lead-free piezoelectric ceramics influenced by defect complexes | |
| CN101786880B (en) | Sodium potassium niobate-potassium lithium niobate piezoelectric ceramics and preparation method thereof | |
| Said et al. | Dielectric, pyroelectric, and ferroelectric properties of gadolinium doped Sr0. 53Ba0. 47Nb2O6 ceramic | |
| Yamatoh et al. | Polymerizable complex synthesis of lead-free ferroelectric Na0. 5Bi0. 5TiO3 suppressing evaporation of sodium and bismuth | |
| Rai et al. | Dielectric and piezoelectric studies of Fe doped PLZT ceramics | |
| CN102503410B (en) | Preparation method of barium strontium titanate-lead titanate pyroelectric ceramic | |
| CN103981573A (en) | Method for improving curie temperature of perovskite structure ferroelectric material | |
| CN104098330B (en) | Post growth annealing is adopted to prepare the method for high-performance barium strontium titanate pyroelectric ceramics | |
| Shannigrahi et al. | Structural and dielectric properties of Nd modified Pb (Zr0. 60Ti0. 40) O3 ceramics | |
| CN102503422B (en) | Titanium-niobium-magnesium-indium acid lead pyroelectric ceramic and preparation method thereof | |
| Chauhan et al. | Dielectric and piezoelectric properties of sol–gel derived Ca doped PbTiO3 | |
| Ahn et al. | Perovskite phase developments and dielectric characteristics in barium-substituted lead zinc tantalate system | |
| Ramesh et al. | Dielectric properties of lead indium niobate ceramics synthesized by conventional solid state reaction method | |
| Rai et al. | Investigation of structural and dielectric properties of (La, Fe)-doped PZT ceramics | |
| Yu et al. | Phase transition and relaxor nature of BaTiO3 ceramics induced by Li/Ga co-doping | |
| Choudhary et al. | Phase transition in Bi-modified PLZT ferroelectrics | |
| CN1683273A (en) | Method for high temperature quick synthesizing blender or compound titanate ceramic powder | |
| PŁOŃSKA et al. | Application of the sol-gel method to the synthesis of ferroelectric nanopowders (Pb1-xLax)(Zr0. 65Ti0. 35), 0.06≤ x≤ 0.1 | |
| Zhang et al. | Composition designing and sintering behavior tailoring in [(Ba1− xCax) 0.995 Eu0. 005](Ti1− yHfy) O3 multifunctional piezoceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130731 Termination date: 20161102 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |