CN102260075B - 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 PDF

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CN102260075B
CN102260075B CN 201110138132 CN201110138132A CN102260075B CN 102260075 B CN102260075 B CN 102260075B CN 201110138132 CN201110138132 CN 201110138132 CN 201110138132 A CN201110138132 A CN 201110138132A CN 102260075 B CN102260075 B CN 102260075B
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barium strontium
strontium calcium
ceramic material
preparation
calcium titanate
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CN102260075A (en
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毛朝梁
董显林
王根水
曹�盛
姚春华
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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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 plasticstripping; 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

A kind of barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof
Technical field
The present invention relates to a kind of barium strontium calcium titanate 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 the 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 to be thinned to tens microns, this is that temperature variation is larger in the time of can making the same infrared heat of absorption owing to thinner substrate, thus the sensitivity that can improve device; In addition, need extra electric field during owing to the work of BST pottery, substrate is thinner, and required voltage is just lower, 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 less, easier attenuate, so size of microcrystal is 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, barium-strontium titanate-based pyroelectric ceramic material being satisfied make the requirement of non-refrigerating infrared focal plane performance of devices, is a difficult problem of needing solution in the research of present BST base pyroelectric ceramic material badly.
Summary of the invention
For solve exist the large and size of microcrystal of size of microcrystal to reduce when prior art prepares the BST material after, the problem such as balance choice between the close grain particle diameter that exists and the high pyroelectric property, the invention provides a kind of barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof, to satisfy present non-refrigerating infrared focal plane device to the requirement of 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 titanate 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 titanate 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, adjust the pH value of solution 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, then the pH value of regulator solution is 5.5～6.5, obtains precursor solution;
B) precursor solution that a) makes at 750～850 ℃ of lower calcining steps 1～2 hour obtains barium strontium calcium powder body;
C) with step b) the barium strontium calcium powder body that makes pulverizes, sieves, wet ball grinding;
D) with step c) oven dry of the barium strontium calcium powder body that makes, add binding agent, through granulation, ageing, sieve, moulding, plastic removal step, make barium strontium calcium base substrate;
E) with steps d) barium strontium calcium base substrate sintering under oxygen of making: 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, namely get barium strontium calcium titanate pyroelectric ceramic material.
Described water-soluble organic acid is recommended as acetic acid or water-soluble alpha hydroxy acid.
Described water-soluble alpha hydroxy acid is recommended as lactic acid.
Step c) barium strontium calcium powder body was recommended 40～200 mesh sieves in before carrying out wet ball grinding.
Step c) the wet ball grinding condition in 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 Ball-milling Time is 24～48 hours, and described ball-milling medium is recommended as agate ball.
Steps d) it is 6%～7% polyvinyl alcohol (PVA) solution that the binding agent in is recommended as mass concentration, and the add-on of PVA solution is 5%～6% of barium strontium calcium powder weight.
Steps d) digestion time in is recommended as 22～26 hours.
Steps d) the plastic removal condition in is recommended as 750～850 ℃ of plastic removals 1～2 hour.
Compared with prior art, adopt the barium strontium calcium titanate pyroelectric ceramic material of method preparation of the present invention not only to have size of microcrystal little (about 2.8 microns), specific inductivity large (10 4The order of magnitude), and has higher pyroelectric property, can satisfy and make the requirement of non-refrigerating infrared focal plane performance of devices, 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
Fig. 1 is the stereoscan photograph of barium strontium calcium titanate pyroelectric ceramic material after surface finish, thermal etching that embodiment 1 makes.
Fig. 2 is the change curve of barium strontium calcium titanate pyroelectric ceramic material dielectric constant with temperature under applying direct current electric field of making of embodiment 1.
Fig. 3 is barium strontium calcium titanate pyroelectric ceramic material dielectric loss variation with temperature graphic representation under applying direct current electric field that embodiment 1 makes.
Fig. 4 is that the barium strontium calcium titanate pyroelectric ceramic material that embodiment 1 makes adopts the pyroelectric coefficient of Quasi-static Method test with the change curve of 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, adjust the pH value of solution 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, then the pH value to 6 of regulator solution obtains barium strontium calcium precursor solution.
Barium strontium calcium precursor solution 800 ℃ of dinectly brunings 2 hours, is 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 technique again; The mass ratio of ball milling material, ball-milling medium (agate ball) and deionized water is 1: 2.0: 0.8, and 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 barium strontium calcium powder weight, granulation, and 20 mesh sieves are crossed in ageing 24 hours, and moulding at 800 ℃ of plastic removals, namely makes barium strontium calcium base substrate; With barium strontium calcium base substrate sintering under oxygen, the condition of sintering 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 is at 650～750 ℃ of lower insulations 20～40 minutes, the dielectric of specimen and pyroelectric property under direct-current biasing.
Fig. 1 is the SEM photo of barium strontium calcium titanate pyroelectric ceramic material after surface finish, thermal etching that present embodiment makes, and 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.
Fig. 2 is the change curve of barium strontium calcium titanate pyroelectric ceramic material dielectric constant with temperature under applying direct current electric field of making of present embodiment, and 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 is to high-temperature mobile, and specific inductivity descends.
Fig. 3 is barium strontium calcium titanate pyroelectric ceramic material dielectric loss variation with temperature graphic representation under applying direct current electric field that present embodiment makes, 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%.
Fig. 4 is that the barium strontium calcium titanate pyroelectric ceramic material that present embodiment makes adopts the pyroelectric coefficient of Quasi-static Method test with the change curve of temperature and applying direct current electric field, as seen from Figure 4: electric field so that the pyroelectric coefficient peak to high-temperature mobile, the pyroelectric coefficient peak value increases afterwards first and reduces, under the 400V/mm electric field, the pyroelectric coefficient peak value is maximum, is 23.7 * 10 -8Ccm -2K -1
In sum, adopt the barium strontium calcium titanate pyroelectric ceramic material of the inventive method preparation not only to have size of microcrystal little (about 2.8 microns), specific inductivity large (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 and make the requirement of non-refrigerating infrared focal plane performance of devices.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 (8)

1. the preparation method of a barium strontium calcium titanate pyroelectric ceramic material, described material 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; It is characterized in that described preparation method 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, adjust the pH value of solution 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, then the pH value of regulator solution is 5.5～6.5, obtains precursor solution;
B) precursor solution that a) makes at 750～850 ℃ of lower calcining steps 1～2 hour obtains barium strontium calcium powder body;
C) with step b) the barium strontium calcium powder body that makes pulverizes, sieves, wet ball grinding;
D) with step c) oven dry of the barium strontium calcium powder body that makes, add binding agent, through granulation, ageing, sieve, moulding, plastic removal step, make barium strontium calcium base substrate;
E) with steps d) barium strontium calcium base substrate sintering under oxygen of making: 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, namely get barium strontium calcium titanate pyroelectric ceramic material.
2. the preparation method of barium strontium calcium titanate pyroelectric ceramic material according to claim 1, it is characterized in that: described water-soluble organic acid is acetic acid or water-soluble alpha hydroxy acid.
3. the preparation method of barium strontium calcium titanate pyroelectric ceramic material according to claim 2, it is characterized in that: described water-soluble alpha hydroxy acid is lactic acid.
4. the preparation method of barium strontium calcium titanate pyroelectric ceramic material according to claim 1 is characterized in that: barium strontium calcium powder body mistake 40～200 mesh sieves before carrying out wet ball grinding step c).
5. the preparation method of barium strontium calcium titanate pyroelectric ceramic material according to claim 1, it is characterized in that, step c) the wet ball grinding condition in 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, Ball-milling Time is 24～48 hours, and described ball-milling medium is agate ball.
6. the preparation method of barium strontium calcium titanate pyroelectric ceramic material according to claim 1, it is characterized in that: the binding agent steps d) is that mass concentration is 6%～7% polyvinyl alcohol (PVA) solution, and the add-on of PVA solution is 5%～6% of barium strontium calcium powder weight.
7. the preparation method of barium strontium calcium titanate pyroelectric ceramic material according to claim 1, it is characterized in that: the digestion time steps d) is 22～26 hours.
8. the preparation method of barium strontium calcium titanate pyroelectric ceramic material according to claim 1 is characterized in that: the plastic removal condition steps d) is 750～850 ℃ of plastic removals 1～2 hour.
CN 201110138132 2011-05-26 2011-05-26 Barium strontium calcium titanate pyroelectric ceramic material and preparation method thereof Active CN102260075B (en)

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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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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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