CN102260075A - Barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof - Google Patents
Barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof Download PDFInfo
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- CN102260075A CN102260075A CN2011101381327A CN201110138132A CN102260075A CN 102260075 A CN102260075 A CN 102260075A CN 2011101381327 A CN2011101381327 A CN 2011101381327A CN 201110138132 A CN201110138132 A CN 201110138132A CN 102260075 A CN102260075 A CN 102260075A
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- barium strontium
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Abstract
The invention discloses a barium strontium calcium titanate pyroelectric ceramic material and a preparation method thereof. The barium strontium calcium titanate pyroelectric ceramic material has a composition general formula of Ba0.6(1-x)-(x-0.001)/2(Sr0.3Ca0.1)1-xYxTi0.999Mn0.001O3, wherein x is not less than 0.001 and not more than 0.010. The preparation method comprises the following steps of: dissolving the Ti(OCH(CH3)2)4 in a mixed solution of organic acid and water; adjusting a pH value to 7.5-8.5; dissolving the Ba(CH3COO)2, Sr(CH3COO)2.0.5H2O, Ca(NO3)2, Y(NO3)3 and Mn(NO3)2 in the water; mixing the two solutions, stirring and adding water to prepare the solution with the mass concentration of 10-20 percent; then adjusting the pH value of the solution to 5.5-6.5; obtaining a precursor solution, and calcining, smashing, screening with a screen and refining; then drying, adding a binder, and executing the steps of pelleting, ageing, screening with the screen, molding and plastic stripping; and finally sintering in the oxygen. The barium strontium calcium titanate pyroelectric ceramic material prepared by the method has a small grain size, large dielectric constant, small dielectric loss, and higher pyroelectric performance, and has the advantages of simple preparation method, short period, low cost and the like, so that the material is suitable for mass production and can meet the industrialization demand.
Description
Technical field
The present invention relates to a kind of barium strontium calcium pyroelectric ceramic material and preparation method thereof, belong to the pyroelectric ceramic material technical field.
Background technology
Strontium-barium titanate (BST, Ba
1-xSr
xTiO
3, 0≤x≤1) and stupalith is owing to have characteristics such as adjustable Curie temperature, high-k, low-dielectric loss, makes it become very important thermoelectric type non-refrigerating infrared focal plane candidate material.
When using the BST pyroelectric ceramic material to make the non-refrigerating infrared focal plane device, it need be thinned to tens microns, this is because thin more substrate can make when absorbing same infrared heat temperature variation bigger, thus the sensitivity that can improve device; In addition, need extra electric field during owing to the work of BST pottery, substrate is thin more, and required voltage is just low more, has also brought advantage for its application.The attenuate of stupalith depends primarily on the size of microcrystal of pottery, and size of microcrystal is more little, easy more attenuate, so size of microcrystal is a very important element in the ceramic micro-structure.In the BST pottery, after size of microcrystal reduced, its dielectric properties and pyroelectric property can have greatly changed.Therefore there is the problem that balance is accepted or rejected between a close grain particle diameter and the high pyroelectric property.So, how effectively to avoid the contradiction between close grain particle diameter and the high pyroelectric property, making barium-strontium titanate-based pyroelectric ceramic material can satisfy the performance requriements of making the non-refrigerating infrared focal plane device, is a difficult problem of needing solution in the research of present BST base pyroelectric ceramic material badly.
Summary of the invention
After existing size of microcrystal to reduce during for solution prior art for preparing BST material than big and size of microcrystal, problem such as balance choice between close grain particle diameter that exists and the high pyroelectric property, the invention provides a kind of barium strontium calcium pyroelectric ceramic material and preparation method thereof, to satisfy of the requirement of present non-refrigerating infrared focal plane device to the BST material.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of barium strontium calcium pyroelectric ceramic material, its composition general formula is: Ba
0.6 (1-x)-(x-0.001)/2(Sr
0.3Ca
0.1)
1-xY
xTi
0.999Mn
0.001O
3, 0.001≤x≤0.010.
The preparation method of described barium strontium calcium pyroelectric ceramic material comprises the steps:
A) measure the Ti (OCH (CH of stoichiometric ratio according to general formula
3)
2)
4, Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2, with Ti (OCH (CH
3)
2)
4Be dissolved in the mixing solutions of water-soluble organic acid and water, the pH value of adjusting solution is between 7.5～8.5; Again with Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2Soluble in water; Above two kinds of solution are mixed, stir and add water to be made into mass concentration be 10%～20% mixing solutions, the pH value of regulator solution is 5.5～6.5 then, obtains precursor solution;
B) precursor solution that a) makes at 750～850 ℃ of following calcining steps is 1～2 hour, obtains barium strontium calcium powder body;
C) the barium strontium calcium powder body that step b) is made is pulverized, is sieved, wet ball grinding;
D) oven dry of the barium strontium calcium powder body that step c) made adds binding agent, through granulation, ageing, sieve, moulding, plastic removal step, make barium strontium calcium base substrate;
E) the barium strontium calcium base substrate sintering under oxygen that step d) is made: the speed with 1～4 ℃/min heats up; Begin logical oxygen when being warmed up to 800～1000 ℃, oxygen flow is 1～3L/min; When being warmed up to 1400～1450 ℃, be incubated 1～2 hour; Cool to room temperature with the furnace, close oxygen, promptly get barium strontium calcium pyroelectric ceramic material.
Described water-soluble organic acid is recommended as acetate or water-soluble alpha hydroxy acid.
Described water-soluble alpha hydroxy acid is recommended as lactic acid.
Barium strontium calcium powder body was recommended 40～200 mesh sieves in the step c) before carrying out wet ball grinding.
Wet ball grinding condition in the step c) is recommended as: the mass ratio of ball milling material and ball-milling medium and deionized water is 1: 1.5: 0.5～1: 2.0: 1.0, and the ball milling time is 24～48 hours, and described ball-milling medium is recommended as agate ball.
It is 6%～7% polyvinyl alcohol (PVA) solution that binding agent in the step d) is recommended as mass concentration, and the add-on of PVA solution is 5%～6% of a barium strontium calcium powder physique amount.
Digestion time in the step d) is recommended as 22～26 hours.
Plastic removal condition in the step d) is recommended as 750～850 ℃ of plastic removals 1～2 hour.
Compared with prior art, adopt the barium strontium calcium pyroelectric ceramic material of method preparation of the present invention not only to have size of microcrystal little (about 2.8 microns), specific inductivity big (10
4The order of magnitude), and has higher pyroelectric property, can satisfy the performance requriements of making the non-refrigerating infrared focal plane device, effectively solved the contradiction between fine grain size and the high pyroelectric property; And preparation method of the present invention is simple, need not specific installation, and low cost and other advantages is fit to large-scale production, can satisfy the industrialization demand.
Description of drawings
The stereoscan photograph of barium strontium calcium pyroelectric ceramic material after surface finish, thermal etching that Fig. 1 makes for embodiment 1.
The change curve of barium strontium calcium pyroelectric ceramic material dielectric constant with temperature under applying direct current electric field that Fig. 2 makes for embodiment 1.
The barium strontium calcium pyroelectric ceramic material that Fig. 3 makes for embodiment 1 under applying direct current electric field dielectric loss with the variation of temperature graphic representation.
The barium strontium calcium pyroelectric ceramic material that Fig. 4 makes for embodiment 1 adopts the change curve of the pyroelectric coefficient of quasistatic method test with temperature and applying direct current electric field.
Specific implementation method
The present invention is described in further detail and completely below in conjunction with embodiment.
Embodiment 1
According to Formula B a
0.5928(Sr
0.3Ca
0.1)
0.993Y
0.007Ti
0.999Mn
0.001O
3Measure the Ti (OCH (CH of stoichiometric ratio
3)
2)
4, Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2, with Ti (OCH (CH
3)
2)
4Be dissolved in the mixing solutions of lactic acid and water, the pH value of adjusting solution is between 8; Again with Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2Soluble in water; Afterwards above two kinds of solution are mixed, stir and add water to be made into mass concentration be 15% mixing solutions, the pH value to 6 of regulator solution obtains barium strontium calcium precursor solution then.
Barium strontium calcium precursor solution was directly calcined 2 hours at 800 ℃, obtained barium strontium calcium powder body.Barium strontium calcium powder body was ground 40 mesh sieves, made the refinement of barium strontium calcium powder body with wet ball grinding technology again; The mass ratio of ball milling material, ball-milling medium (agate ball) and deionized water is 1: 2.0: 0.8, and the ball milling time is 48 hours.
Oven dry adds PVA solution (mass concentration is 6.0%) binding agent, and the add-on of PVA solution is 6% of a barium strontium calcium powder physique amount, granulation, and 20 mesh sieves are crossed in ageing 24 hours, and moulding at 800 ℃ of plastic removals, promptly makes barium strontium calcium base substrate; With barium strontium calcium base substrate sintering under oxygen, the agglomerating condition is: the speed with 2.5 ℃/min heats up; Begin logical oxygen when being warmed up to 800 ℃, oxygen flow is 2L/min; When being warmed up to 1450 ℃, be incubated 2 hours; Cool to room temperature with the furnace, close oxygen.
The sample that sinters is processed into the size that needs, ultrasonic cleaning, silk screen printing silver slurry, oven dry, insulation is 20～40 minutes under 650～750 ℃, the dielectric of specimen and pyroelectric property under direct-current biasing.
The SEM photo of barium strontium calcium pyroelectric ceramic material after surface finish, thermal etching that Fig. 1 makes for present embodiment, as seen from Figure 1: the size of microcrystal of pottery is little, and the average crystal grain particle diameter is about 2.8 μ m.
The change curve of barium strontium calcium pyroelectric ceramic material dielectric constant with temperature under applying direct current electric field that Fig. 2 makes for present embodiment, as seen from Figure 2: the Curie temperature of pottery is near room temperature, and specific inductivity is 10
4The order of magnitude, along with the increase of electric field, Curie temperature moves to high temperature, and specific inductivity descends.
The barium strontium calcium pyroelectric ceramic material that Fig. 3 makes for present embodiment under applying direct current electric field dielectric loss with the variation of temperature graphic representation, as seen from Figure 3: electric field has reduced ceramic dielectric loss, under the 400V/mm electric field, the dielectric loss at Curie temperature place is lower than 1%.
The barium strontium calcium pyroelectric ceramic material that Fig. 4 makes for present embodiment adopts the change curve of the pyroelectric coefficient of quasistatic method test with temperature and applying direct current electric field, as seen from Figure 4: electric field makes the pyroelectric coefficient peak move to high temperature, the pyroelectric coefficient peak value increases afterwards earlier and reduces, under the 400V/mm electric field, pyroelectric coefficient peak value maximum is 23.7 * 10
-8Ccm
-2K
-1
In sum, adopt the barium strontium calcium pyroelectric ceramic material of the inventive method preparation not only to have size of microcrystal little (about 2.8 microns), specific inductivity big (10
4The order of magnitude), dielectric loss little (＜1%), and have higher pyroelectric property, when the 400V/mm bias field, its pyroelectric coefficient can reach 23.7 * 10
-8Ccm
-2K
-1, survey the figure of merit and can reach 3.8 * 10
-5Pa
-1/2, can satisfy the performance requriements of making the non-refrigerating infrared focal plane device.And preparation method of the present invention simple, need not specific installation, low cost and other advantages, be fit to large-scale production, can satisfy the industrialization demand.
Be necessary to be pointed out that at this: above embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (9)
1. a barium strontium calcium pyroelectric ceramic material is characterized in that, has following composition general formula: Ba
0.6 (1-x)-(x-0.001)/2(Sr
0.3Ca
0.1)
1-xY
xTi
0.999Mn
0.001O
3, 0.001≤x≤0.010.
2. the preparation method of the described barium strontium calcium of claim 1 pyroelectric ceramic material is characterized in that, comprises the steps:
A) measure the Ti (OCH (CH of stoichiometric ratio according to general formula
3)
2)
4, Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2, with Ti (OCH (CH
3)
2)
4Be dissolved in the mixing solutions of water-soluble organic acid and water, the pH value of adjusting solution is between 7.5～8.5; Again with Ba (CH
3COO)
2, Sr (CH
3COO)
20.5H
2O, Ca (NO
3)
2, Y (NO
3)
3And Mn (NO
3)
2Soluble in water; Above two kinds of solution are mixed, stir and add water to be made into mass concentration be 10%～20% mixing solutions, the pH value of regulator solution is 5.5～6.5 then, obtains precursor solution;
B) precursor solution that a) makes at 750～850 ℃ of following calcining steps is 1～2 hour, obtains barium strontium calcium powder body;
C) the barium strontium calcium powder body that step b) is made is pulverized, is sieved, wet ball grinding;
D) oven dry of the barium strontium calcium powder body that step c) made adds binding agent, through granulation, ageing, sieve, moulding, plastic removal step, make barium strontium calcium base substrate;
E) the barium strontium calcium base substrate sintering under oxygen that step d) is made: the speed with 1～4 ℃/min heats up; Begin logical oxygen when being warmed up to 800～1000 ℃, oxygen flow is 1～3L/min; When being warmed up to 1400～1450 ℃, be incubated 1～2 hour; Cool to room temperature with the furnace, close oxygen, promptly get barium strontium calcium pyroelectric ceramic material.
3. the preparation method of barium strontium calcium pyroelectric ceramic material according to claim 2 is characterized in that: described water-soluble organic acid is acetate or water-soluble alpha hydroxy acid.
4. the preparation method of barium strontium calcium pyroelectric ceramic material according to claim 3 is characterized in that: described water-soluble alpha hydroxy acid is a lactic acid.
5. the preparation method of barium strontium calcium pyroelectric ceramic material according to claim 2 is characterized in that: barium strontium calcium powder body is crossed 40～200 mesh sieves in the step c) before carrying out wet ball grinding.
6. the preparation method of barium strontium calcium pyroelectric ceramic material according to claim 2, it is characterized in that, wet ball grinding condition in the step c) is: the mass ratio of ball milling material and ball-milling medium and deionized water is 1: 1.5: 0.5～1: 2.0: 1.0, the ball milling time is 24～48 hours, and described ball-milling medium is an agate ball.
7. the preparation method of barium strontium calcium pyroelectric ceramic material according to claim 2, it is characterized in that: the binding agent in the step d) is that mass concentration is 6%～7% polyvinyl alcohol (PVA) solution, and the add-on of PVA solution is 5%～6% of a barium strontium calcium powder physique amount.
8. the preparation method of barium strontium calcium pyroelectric ceramic material according to claim 2 is characterized in that: the digestion time in the step d) is 22～26 hours.
9. the preparation method of barium strontium calcium pyroelectric ceramic material according to claim 2 is characterized in that: the plastic removal condition in the step d) is 750～850 ℃ of plastic removals 1～2 hour.
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| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101812A (en) * | 2006-07-04 | 2008-01-09 | 上海易力禾电子有限公司 | Positive temperature coefficient strontium titanate pressure sensitive resistor and its production process |
| CN101654360A (en) * | 2008-08-19 | 2010-02-24 | 达方电子股份有限公司 | Ceramic powder composition, ceramic material and multilayer ceramic capacitor made thereby |
| CN102060526A (en) * | 2010-12-10 | 2011-05-18 | 四川大学 | Preparation method of manganese and yttrium double-doped barium strontium titanate ceramic material |
| CN102060527A (en) * | 2010-12-10 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Doped and modified barium strontium calcium titanate heat-release pyroelectric ceramic material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101812A (en) * | 2006-07-04 | 2008-01-09 | 上海易力禾电子有限公司 | Positive temperature coefficient strontium titanate pressure sensitive resistor and its production process |
| CN101654360A (en) * | 2008-08-19 | 2010-02-24 | 达方电子股份有限公司 | Ceramic powder composition, ceramic material and multilayer ceramic capacitor made thereby |
| CN102060526A (en) * | 2010-12-10 | 2011-05-18 | 四川大学 | Preparation method of manganese and yttrium double-doped barium strontium titanate ceramic material |
| CN102060527A (en) * | 2010-12-10 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Doped and modified barium strontium calcium titanate heat-release pyroelectric ceramic material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| DAE-SEOK KANG等: "Dielectric and pyroelectric properties of barium strontium calcium titanate ceramics, Dae-Seok Kang et al，Journal of the European Ceramic Society", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
Cited By (1)
| 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 |
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