CN108314445A - A kind of barium dititanate and preparation method thereof with wide Curie's warm area - Google Patents

A kind of barium dititanate and preparation method thereof with wide Curie's warm area Download PDF

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CN108314445A
CN108314445A CN201810437307.6A CN201810437307A CN108314445A CN 108314445 A CN108314445 A CN 108314445A CN 201810437307 A CN201810437307 A CN 201810437307A CN 108314445 A CN108314445 A CN 108314445A
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barium
warm area
source solution
dititanate
curie
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CN108314445B (en
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戴英
刘俊君
裴新美
陈文�
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Wuhan University of Technology WUT
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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Abstract

The present invention relates to a kind of barium dititanates and preparation method thereof with wide Curie's warm area, are prepared by following methods：1) one kind in acetylacetone,2,4-pentanedione cerium hydrate, six nitric hydrate samariums, six nitric hydrate europiums is dissolved in barium acetate in glacial acetic acid jointly and obtains barium source solution；2) butyl titanate is dissolved in ethylene glycol monomethyl ether and obtains titanium source solution；3) barium source solution is mixed with titanium source solution, gained colloidal sol is aged in air, dries and obtains xerogel, then through pre-burning, ball milling, be dried to obtain two barium carbonate powders；4) two barium carbonate powders are granulated successively, are dry-pressing formed, dumping, pressureless sintering, obtain barium dititanate.Barium dititanate provided by the invention has wider Curie's warm area, meets the design requirement of high temperature ferro-electric device, and have the advantages that single phase property is good.

Description

A kind of barium dititanate and preparation method thereof with wide Curie's warm area
Technical field
The invention belongs to technical field of ceramic material, and in particular to a kind of barium dititanate with wide Curie's warm area and Preparation method.
Background technology
Ferroelectric material has a variety of good characteristics such as piezoelectricity, pyroelectric, ferroelectricity, electro-optical characteristic, acousto-optic performance, It is widely used in modern industry, wherein ferroelectric memory, driver, sensor and pyroelectric detector etc. often need It is used in hot environment, and when operating temperature is higher than the Curie temperature of ferroelectric material, general ferroelectric material dielectric constant is bright Aobvious decline, dielectric loss drastically increase, and can not work normally.
Two barium titanates have the advantages that high-curie temperature (about 470 DEG C), unleaded, but since Curie's warm area is relatively narrow, only exist There are good dielectric properties in the relatively narrow warm area of vicinity of Curie temperatures, to make barium dititanate device in wider high temperature range It can work normally, need the Curie's warm area for widening barium dititanate, it is made to meet the requirement of high temperature ferro-electric device.Mesh Before to prepare the common method of barium dititanate be with BaCO3、TiO2It is obtained by conventional solid reaction method for raw material, in this base Single valence doped chemical is added on plinth replaces Ti4+To widen Curie's warm area, but due to two barium titanate Thermodynamically stable sections compared with It is narrow, there are powder purities in solid phase method preparation process it is low, sintering temperature is high, phase stability is poor the shortcomings of, and ceramics obtained Often there is the shortcomings of relatively low Curie's peak value, Curie's wide temperature region effect unobvious.
When the present invention is doped substitution using two barium titanate of changeable valence rare earth element pair A or B, the difference of ionic radius Distortion of lattice, the change of cell parameter can be caused to generate significantly the performance for belonging to two barium titanate of monocline of low symmetrical centre It influences, the ingredient fluctuation and valence state fluctuation that the introducing of valence variation element is brought cause to generate different ferroelectricities in barium dititanate Microcell and non-ferroelectricity microcell.Compared with barium titanate, the crystal structure of two barium titanates is complex, and there are three kinds of different TiO6Eight The particularity of face body, structure causes its performance change more sensitive to Doped ions.Meanwhile it being adulterated using valence variation element, two titaniums There are the Doped ions of different valence state in sour titanate ceramics, compared with single valence ion doping, the semidiameter of different valence state ion Different the position of substitution caused by different, valence state fluctuation further enhance the disperse degree of structure.These factors make two barium titanates exist The ferroelectric phase transition type of near Curie temperature is changed into dispersivity ferroelectric phase transition by normal ferroelectric phase transition, is shown being situated between in temperature spectrum The feature of dielectric peak stretching.Using sol-gal process synthetic powder, sinterable while reducing sintering temperature to obtain crystal grain thin Small ceramics, a large amount of crystal boundary can hinder the rotation of electricdomain and improve dispersivity, be appraised at the current rate on this basis using Ce, Sm, Eu etc. Element doping, by the adjusting to preparation technology parameters such as material rate, powder synthesis temperature, sintering schedule, atmosphere, control becomes The redox reaction of valence element, Ce when making doping3+With Ce4+、Sm2+With Sm3+、Eu2+With Eu3+Ion difference is in proper proportions It is present in ceramics, further promotes two barium titanate phase transformations to change to diffused phase transition, keep its Curie's warm area significantly broadened, meets The design requirement of high temperature ferro-electric device.
Invention content
It is a kind of with width the technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide The barium dititanate and preparation method thereof of Curie's warm area.
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of barium dititanate with wide Curie's warm area is provided, is prepared by following methods：
1) one kind in acetylacetone,2,4-pentanedione cerium hydrate, six nitric hydrate samariums, six nitric hydrate europiums is jointly molten with barium acetate Barium source solution is obtained in glacial acetic acid；
2) butyl titanate is dissolved in ethylene glycol monomethyl ether and obtains titanium source solution；
3) barium source solution obtained by step 1) is mixed with titanium source solution obtained by step 2), makes molar ratio in gained mixed solution Ba：Ti=1：2,10~14h of stirring obtains colloidal sol, and gained colloidal sol be aged in air, dry and obtains xerogel, then passes through in advance Burning, is dried to obtain two barium carbonate powders at ball milling；
4) two barium carbonate powders obtained by step 3) are granulated successively, dry-pressing formed, dumping, pressureless sintering, obtain two Barium titanate ceramics.
By said program, in step 1) the barium source solution molar ratio of contained cerium, samarium or europium and barium element be 0.002~ 0.008：1.
By said program, a concentration of 0.8~1.3mol/L of barium ions in step 1) the barium source solution.
By said program, the step 2) butyl titanate is butyl titanate with ethylene glycol monomethyl ether molar ratio：Ethylene glycol Methyl ether=1：3.5~6.
By said program, the step 3) digestion time is 4~6h.
By said program, step 3) the stoving process condition is：In 100~120 DEG C dry 12~for 24 hours.
By said program, step 3) the pre-sinter process condition is：800 are warming up to the rate of 4 DEG C/min at room temperature~ 1000 DEG C, keep the temperature 3~5h.
By said program, step 3) the ball-milling technology condition is：Drum's speed of rotation is 480~540 revs/min, ball milling Time is 10~12h.
By said program, the PVA of two barium titanate powder weights 5% is added in step 4) granulation process, and 100 mesh are crossed after granulation Sieve.
By said program, step 4) the dry-pressing formed pressure is 150~200MPa, dwell time 1min.
By said program, step 4) the binder removal condition is：600 are warming up to the rate of 1 DEG C/min at room temperature~ 800 DEG C, keep the temperature 2~4h.
By said program, step 4) the non-pressure sintering technology condition is：It is warming up at room temperature with the rate of 4 DEG C/min 1150~1200 DEG C, keep the temperature 3~6h.
The present invention also provides the preparation methods of the above-mentioned barium dititanate with wide Curie's warm area, are as follows：
1) butyl titanate is dissolved in ethylene glycol monomethyl ether and obtains titanium source solution；
2) one kind in acetylacetone,2,4-pentanedione cerium hydrate, six nitric hydrate samariums, six nitric hydrate europiums is dissolved in ice with barium acetate Barium source solution is obtained in acetic acid；
3) titanium source solution obtained by step 1) is mixed with barium source solution obtained by step 2), 10~14h of stirring obtains colloidal sol, will Gained colloidal sol is aged in air, dries and obtains xerogel, then through pre-burning, ball milling, be dried to obtain two barium carbonate powders；
4) two barium carbonate powders obtained by step 3) are granulated successively, dry-pressing formed, dumping, pressureless sintering, obtain two Barium titanate ceramics.
For the present invention using glacial acetic acid as solvent and stabilizer, ethylene glycol monomethyl ether is diluent, and two metatitanic acid barium precursors of configuration are molten Glue, ageing, drying after obtain xerogel, ground successively, pre-burning, ball milling, granulation, dry-pressing formed, dumping, sintering, obtain The barium dititanate of different ions doping.The changeable valence rare earths elements such as samarium, cerium and europium are chosen as doped chemical, while using molten Sol-gel synthesizes two barium carbonate powders, and sintering obtains the crystal grain ceramics high compared with thin, consistency.Doped chemical is in substitution Ba2+、 Ti4+Cause distortion of lattice when ion, the change of cell parameter is to belonging to the performance of two barium titanate of monocline of low symmetrical centre Make a significant impact, and due in two barium titanates titanium atom exist (specifically, the primitive cell structure of two barium titanates with three kinds of states The middle TiO to distort there are 3 kinds6Octahedron, to be not Ti1O6、Ti2O6、Ti3O6, for these three octahedrons, Ti atoms Residing chemical environment is different), valence variation element doping extremely be easy to cause ingredient fluctuation and valence state fluctuation, makes two barium titanates Different ferroelectricity microcells and non-ferroelectricity microcell are generated in ceramics, cause two barium titanates that diffused phase transition, while collosol and gel occurs The ceramics that method synthetic powder obtains have a large amount of crystal boundary, hinder ferroelectric domain movement and reinforce dispersivity, these factors are effectively opened up Wide Curie's warm area of barium dititanate.
The beneficial effects of the present invention are：1, barium dititanate provided by the invention has wider Curie's warm area, full The design requirement of sufficient high temperature ferro-electric device, and have the advantages that single phase property is good.2, preparation method work provided by the invention Skill is simple, low for equipment requirements, and powder synthesis and ceramic sintering temperature are relatively low, and doping is easily controllable, it is easy to accomplish volume production.
Description of the drawings
Fig. 1 is the X ray diffracting spectrum of the barium dititanate prepared by comparative example 1 of the present invention and embodiment 1-3；
Fig. 2 is the dielectric constant with temperature variation diagram of the barium dititanate prepared by comparative example 1 and embodiment 1-3.
Specific implementation mode
To make those skilled in the art more fully understand technical scheme of the present invention, below in conjunction with the accompanying drawings to the present invention make into One step is described in detail.
Comparative example 1
Barium dititanate is prepared, is as follows：
7.740g barium acetates are weighed, 25mL glacial acetic acids is dissolved in and obtains baric solution, 20.838g butyl titanates is weighed and is dissolved in Titaniferous solution is obtained in 20mL ethylene glycol monomethyl ethers, and baric solution and titaniferous solution are then mixed into (molar ratio Ba under room temperature:Ti= 1：2), stirring 12h obtains two barium titanate precursor sols, gained colloidal sol is placed in air after being aged 4h, is put into 120 DEG C of electric heating Drying for 24 hours, obtains two metatitanic acid barium precursor xerogel, pre-burning is carried out after xerogel is ground, at room temperature with 4 in air dry oven DEG C/rate of min is warming up at 850 DEG C and keeps the temperature 3h, obtains two barium carbonate powders, by powder ball milling 10h, (drum's speed of rotation is 540 revs/min), then the good slurry of ball milling is dried, the PVA of two barium carbonate powder 5wt% of addition is granulated, after granulation It sieves with 100 mesh sieve, then uses dry-pressing formed method, sequin green body is made in pressurize 1min at 150MPa, and green body is carried out Dumping, concrete technology condition are：600 DEG C of heat preservation 2h are warming up to the rate of 1 DEG C/min at room temperature, is sintered, has after dumping Body technology condition is：1170 DEG C are warming up to the rate of 4 DEG C/min at room temperature, 3h is kept the temperature, obtains barium dititanate.
Use Philips companies of model Holland PANalytical X ' Pert PW3050/60 type X-ray diffractometers pair Ceramics obtained by this comparative example carry out constituent analysis.Fig. 1 (a) is the XRD diagram that comparative example of the present invention prepares ceramics.By Fig. 1 (a) and figure BaTi in 12O5Standard card compares it is found that ceramics prepared by this comparative example are two barium titanate of pure phase, and no other dephasigns occur.
By barium dititanate sanding and polishing obtained by this comparative example, two sides applies silver paste, and heat preservation 20min is burnt at 800 DEG C Silver electrode.With Agilent HP1294A ac resistance analysis instrument to carrying out the temperature test that is situated between by the ceramics after silver.Fig. 2 (a) is the present invention Comparative example prepares Jie thermogram of the ceramics at 100kHz, it can be seen from the figure that Curie temperature is 466 DEG C, corresponding Jie's temperature Peak is relatively narrow.
Embodiment 1
Preparing has the barium dititanate of wide Curie's warm area, is as follows：
7.740g barium acetates and six nitric hydrate samariums of 0.040g are dissolved in 25mL glacial acetic acids and obtain barium source solution, it will 20.838g butyl titanates, which are dissolved in 20mL ethylene glycol monomethyl ethers, obtains titanium source solution, then by barium source solution and titanium source under room temperature Solution mixes (molar ratio Ba:Ti:Sm=1:2:0.003), stirring 12h obtains two barium titanate precursor sols, by gained colloidal sol It is placed in air after being aged 4h, is put into drying in 120 DEG C of electric drying oven with forced convections and for 24 hours, obtains two metatitanic acid barium precursor xerogel, Pre-burning is carried out after xerogel is ground, and is warming up at 850 DEG C with the rate of 4 DEG C/min keeps the temperature 3h at room temperature, obtain two barium titanates Then the good slurry of ball milling is dried, adds two metatitanic acids by powder by powder ball milling 10h (drum's speed of rotation is 540 revs/min) The PVA of barium powder 5wt% is granulated, and is sieved with 100 mesh sieve after granulation, is then used dry-pressing formed method, is protected at 150MPa Sequin green body is made in pressure 1min, green body is carried out dumping, concrete technology condition is：It is heated up at room temperature with the rate of 1 DEG C/min To 600 DEG C of heat preservation 2h, it is sintered after dumping, concrete technology condition is：At room temperature 1170 are warming up to the rate of 4 DEG C/min DEG C, 3h is kept the temperature, barium dititanate is obtained.
Use Philips companies of model Holland PANalytical X ' Pert PW3050/60 type X-ray diffractometers pair Ceramics obtained by the present embodiment carry out constituent analysis.Fig. 1 (b) is the XRD diagram that the embodiment of the present invention prepares ceramics.By Fig. 1 (b) and figure BaTi in 12O5Standard card compares it is found that ceramics manufactured in the present embodiment are two barium titanate of pure phase, and no other dephasigns occur, samarium Doping does not result in two barium titanates and decomposes.
By barium dititanate sanding and polishing obtained by the present embodiment, two sides applies silver paste, and heat preservation 20min is burnt at 800 DEG C Silver electrode.With Agilent HP1294A ac resistance analysis instrument to carrying out the temperature test that is situated between by the ceramics after silver.Fig. 2 (b) is the present invention Embodiment prepares Jie thermogram of the ceramics at 100kHz, it can be seen from the figure that Curie temperature is 372 DEG C, corresponding Jie's temperature There is apparent widthization at peak compared with Fig. 2 (a), it is known that samarium element doping can widen Curie's warm area of barium dititanate.
Embodiment 2
Preparing has the barium dititanate of wide Curie's warm area, is as follows：
7.740g barium acetates and six nitric hydrate europiums of 0.054g are dissolved in 25mL glacial acetic acids and obtain barium source solution, it will 20.838g butyl titanates, which are dissolved in 20mL ethylene glycol monomethyl ethers, obtains titanium source solution, then by barium source solution and titanium source under room temperature Solution mixes (molar ratio Ba:Ti:Eu=1:2:0.004), stirring 12h obtains two barium titanate precursor sols, by gained colloidal sol It is placed in air after being aged 4h, is put into drying in 120 DEG C of electric drying oven with forced convections and for 24 hours, obtains two metatitanic acid barium precursor xerogel, Pre-burning is carried out after xerogel is ground, and is warming up at 850 DEG C with the rate of 4 DEG C/min keeps the temperature 3h at room temperature, obtain two barium titanates Then the good slurry of ball milling is dried powder ball milling 10h by powder, the PVA of two barium carbonate powder 5wt% of addition is granulated, It is sieved with 100 mesh sieve after granulation, then uses dry-pressing formed method, sequin green body is made in pressurize 1min at 150MPa, by base Body carries out dumping, and concrete technology condition is：600 DEG C of heat preservation 2h are warming up to the rate of 1 DEG C/min at room temperature, are burnt after dumping Knot, concrete technology condition are：1170 DEG C are warming up to the rate of 4 DEG C/min at room temperature, 3h is kept the temperature, obtains barium dititanate.
Use Philips companies of model Holland PANalytical X ' Pert PW3050/60 type X-ray diffractometers pair Ceramics obtained by the present embodiment carry out constituent analysis.Fig. 1 (c) is the XRD diagram that the embodiment of the present invention prepares ceramics.By Fig. 1 (c) and figure BaTi in 12O5Standard card compares it is found that ceramics manufactured in the present embodiment are two barium titanate of pure phase, and no other dephasigns occur, europium Element doping does not result in the decomposition of two barium titanates.
By barium dititanate sanding and polishing obtained by the present embodiment, two sides applies silver paste, and heat preservation 20min is burnt at 800 DEG C Silver electrode.With Agilent HP1294A ac resistance analysis instrument to carrying out the temperature test that is situated between by the ceramics after silver.Fig. 2 (c) is the present invention Embodiment prepares Jie thermogram of the ceramics at 100kHz, it can be seen from the figure that Curie temperature is 364 DEG C, corresponding Jie's temperature There is apparent widthization at peak compared with Fig. 2 (a), it is known that europium adulterates the Curie's warm area that can widen barium dititanate.
Embodiment 3
Preparing has the barium dititanate of wide Curie's warm area, is as follows：
7.740g barium acetates and 0.052g acetylacetone,2,4-pentanediones cerium (III) hydrate be dissolved in 25mL glacial acetic acids to obtain barium source molten 20.838g butyl titanates are dissolved in 20mL ethylene glycol monomethyl ethers and obtain titanium source solution by liquid, then under room temperature by barium source solution and Titanium source solution mixes (molar ratio Ba:Ti:Ce=1:2:0.004), stirring 12h obtains two barium titanate precursor sols, by gained Colloidal sol is placed in air after ageing 4h, is put into drying in 120 DEG C of electric drying oven with forced convections and for 24 hours, it is dry to be obtained two metatitanic acid barium precursors Gel carries out pre-burning after grinding xerogel, is warming up at 900 DEG C with the rate of 4 DEG C/min keeps the temperature 5h at room temperature, obtain two titaniums Then the good slurry of ball milling is dried powder ball milling 10h by sour barium powder, the PVA of two barium carbonate powder 5wt% of addition is carried out It being granulated, is sieved with 100 mesh sieve after granulation, then use dry-pressing formed method, sequin green body is made in pressurize 1min at 150MPa, Green body is subjected to dumping, concrete technology condition is：600 DEG C of heat preservation 2h are warming up to the rate of 1 DEG C/min at room temperature, dumping is laggard Row sintering, concrete technology condition are：1190 DEG C are warming up to the rate of 4 DEG C/min at room temperature, keeps the temperature 6h, obtains two barium titanates pottery Porcelain.
Use Philips companies of model Holland PANalytical X ' Pert PW3050/60 type X-ray diffractometers pair Ceramics obtained by the present embodiment carry out constituent analysis.Fig. 1 (d) is the XRD diagram that the embodiment of the present invention prepares ceramics.By Fig. 1 (d) and figure BaTi in 12O5Standard card compares it is found that ceramics manufactured in the present embodiment are two barium titanate of pure phase, and no other dephasigns occur, cerium Doping does not result in two barium titanates and decomposes.
By barium dititanate sanding and polishing obtained by the present embodiment, two sides applies silver paste, and heat preservation 20min is burnt at 800 DEG C Silver electrode.With Agilent HP1294A ac resistance analysis instrument to carrying out the temperature test that is situated between by the ceramics after silver.Fig. 2 (d) is the present invention Embodiment prepares Jie thermogram of the ceramics at 100kHz, it can be seen from the figure that Curie temperature is 335 DEG C, corresponding Jie's temperature There is apparent widthization at peak compared with Fig. 2 (a), it is known that Ce elements adulterate the Curie's warm area that can widen barium dititanate.

Claims (10)

1. a kind of barium dititanate with wide Curie's warm area, which is characterized in that it is prepared by following methods：
1) one kind in acetylacetone,2,4-pentanedione cerium hydrate, six nitric hydrate samariums, six nitric hydrate europiums is dissolved in ice jointly with barium acetate Barium source solution is obtained in acetic acid；
2) butyl titanate is dissolved in ethylene glycol monomethyl ether and obtains titanium source solution；
3) barium source solution obtained by step 1) is mixed with titanium source solution obtained by step 2), makes molar ratio Ba in gained mixed solution： Ti=1：2,10~14h of stirring obtains colloidal sol, and gained colloidal sol is aged in air, dries and obtains xerogel, then through pre-burning, ball It grinds, be dried to obtain two barium carbonate powders；
4) two barium carbonate powders obtained by step 3) are granulated successively, dry-pressing formed, dumping, pressureless sintering, obtain two metatitanic acids Titanate ceramics.
2. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that the step 1) barium The molar ratio of contained cerium, samarium or europium and barium element is 0.002~0.008 in the solution of source：1；Barium in step 1) the barium source solution Ion concentration is 0.8~1.3mol/L.
3. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that the step 2) titanium Sour four butyl esters are butyl titanate with ethylene glycol monomethyl ether molar ratio：Ethylene glycol monomethyl ether=1：3.5~6.
4. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that step 3) is described old The change time is 4~6h, and the stoving process condition is：In 100~120 DEG C dry 12~for 24 hours.
5. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that step 3) is described pre- Firing technique condition is：800~1000 DEG C are warming up to the rate of 4 DEG C/min at room temperature, keeps the temperature 3~5h.
6. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that step 4) was granulated The PVA that two barium titanate powder weights 5% are added in journey, sieves with 100 mesh sieve after granulation.
7. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that step 4) is described dry Molded pressure is 150~200MPa, dwell time 1min.
8. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that the step 4) row Adhesive process condition is：600~800 DEG C are warming up to the rate of 1 DEG C/min at room temperature, keeps the temperature 2~4h.
9. the barium dititanate with wide Curie's warm area according to claim 1, which is characterized in that the step 4) nothing Pressure sintering process conditions be：1150~1200 DEG C are warming up to the rate of 4 DEG C/min at room temperature, keeps the temperature 3~6h.
10. according to the preparation method of any barium dititanates with wide Curie's warm area of claim 1-9, feature It is, is as follows：
1) butyl titanate is dissolved in ethylene glycol monomethyl ether and obtains titanium source solution；
2) one kind in acetylacetone,2,4-pentanedione cerium hydrate, six nitric hydrate samariums, six nitric hydrate europiums is dissolved in glacial acetic acid with barium acetate In obtain barium source solution；
3) titanium source solution obtained by step 1) is mixed with barium source solution obtained by step 2), 10~14h of stirring obtains colloidal sol, by gained Colloidal sol is aged in air, dries and obtains xerogel, then through pre-burning, ball milling, be dried to obtain two barium carbonate powders；
4) two barium carbonate powders obtained by step 3) are granulated successively, dry-pressing formed, dumping, pressureless sintering, obtain two metatitanic acids Titanate ceramics.
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