CN102674832B - Barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material and preparation method thereof - Google Patents
Barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material and preparation method thereof Download PDFInfo
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- CN102674832B CN102674832B CN 201210149452 CN201210149452A CN102674832B CN 102674832 B CN102674832 B CN 102674832B CN 201210149452 CN201210149452 CN 201210149452 CN 201210149452 A CN201210149452 A CN 201210149452A CN 102674832 B CN102674832 B CN 102674832B
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- free bismuth
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- based lead
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 39
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000005469 granulation Methods 0.000 claims description 34
- 230000003179 granulation Effects 0.000 claims description 34
- 238000009413 insulation Methods 0.000 claims description 24
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000002003 electrode paste Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003985 ceramic capacitor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 4
- 238000001035 drying Methods 0.000 abstract 2
- 238000003825 pressing Methods 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011267 electrode slurry Substances 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 229910052845 zircon Inorganic materials 0.000 abstract 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 230000009466 transformation Effects 0.000 description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- -1 compound ion Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
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Abstract
The invention provides a barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material and a preparation method thereof. The raw materials of the barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material comprise TiO2, BaCO3, Bi2O3 and Cr2O3. The preparation method of the barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material comprises the steps of: mixing TiO2 and BaCO3 with ball zircon and deionized water, sequentially ball-milling, drying, pressing blocks and firing the blocks to obtain pure-phase BaTiO3 powder; and mixing the Bi2O3 and Cr2O3 with the BaTiO3 powder in equal proportions, sequentially ball-milling, drying, granulating and screening, pressing the mixture into test samples,keeping the temperature to be constant at 1350 DEG C for four hours in air, cooling with a furnace and finally coating electrode slurry. The lead-free ferroelectric ceramic material prepared by adopting the preparation method has an obvious relaxation phenomenon and becomes an important candidate material which can replace lead-base relaxation ferroelectric, can be used for producing multilayer ceramic capacitors and has excellent technical and economic effects.
Description
[technical field]
The present invention relates to a kind of unleaded relaxation ferroelectric ceramic material and preparation method, particularly a kind of BaTiO
3The unleaded bismuth-containing relaxation ferroelectric ceramic material of base and preparation method.
[background technology]
Relaxation ferroelectric ceramic is the very noticeable material of a class in the function ceramics extended familys.It has very high specific inductivity, low relatively sintering temperature and be called for short the low temperature coefficient of capacitance that (DPT) causes by " disperse phase transformation " (Diffuse Phase Transition), being considered to might be the laminated ceramic capacitor of new generation excellent important candidate material of holding concurrently technically and economically.Simultaneously, it has big electrostrictive effect and little characteristics such as electric field induced strain hysteresis, zero restoring ability and favorable reproducibility, therefore also has broad application prospects at micro positioner, actuator and smart material and device etc.
European Union had promulgated the strict use regulations of leaded material in electronic ceramics of forbidding in 2006, and leaded relaxation ferroelectric ceramic all can work the mischief to human body and environment when producing and use simultaneously, and therefore, the unleaded relaxation ferroelectric ceramic of the friendly type of development environment is imperative.
Barium titanate is the ferroelectric ceramic(s) that a class has typical perovskite crystal structure, and three ferroelectric phase heights are arranged, that is: two transformation temperatures are arranged near 0 and-80 ℃, and crystalline structure is changed to rhombic system and then to triangle symmetry crystallographic system by tetragonal system respectively; Be higher than about 120 ℃ of Curie temperature, change cubic structure into by tetragonal; When temperature below 120 ℃ the time, crystalline network changes tetragonal into.Therefore, this BaTiO that has disperse phase transformation, cheap and technical maturity
3The unleaded relaxation ferroelectric ceramic material of base causes that people pay close attention to greatly.
At present, many scholars have been arranged to BaTiO
3The unleaded relaxation ferroelectric ceramic material of base has carried out research widely.For example: Bahri etc. find doping Bi
3+Replace Ba
2+Can strengthen BaTiO
3The relaxation behavior.Simultaneously, T.Badapanda etc. has studied BaTiO
3-BaZrO
3The system discovery Ti that replaces of equal value
4+The position also can produce the disperse phase transformation.Lei Cui etc. are with Bi
3+And Al
3+Mix BaTiO simultaneously
3Carry out the electricity price compensation, also obtain relaxation ferroelectric ceramic and carry out the match contrast with the correlation theory model showing that this system meets existing theoretical model.
[summary of the invention]
Technical problem to be solved by this invention provides a kind of new BaTiO
3Unleaded bismuth-containing relaxation ferroelectric ceramic material of base and preparation method thereof, the relaxation ferroelectric ceramic material that makes by the inventive method, not only has tangible relaxation phenomena, and environmentally friendly, might become alternative lead based relaxor ferroelectrics and become the double technically and economically excellent important candidate material of laminated ceramic capacitor.
For achieving the above object, the present invention adopts following technical scheme:
Barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods may further comprise the steps:
Step 1: be 1 according to mol ratio: (0.9 ~ 0.99) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after mixing at 1: 1: 1 after, place retort furnace to form pure phase barium carbonate powder piece in 2 hours 1000 ~ 1150 ℃ of insulations, standby;
Step 3: be 1mol in pure phase barium carbonate powder piece, take by weighing 0.5 ~ 3.0mol%Bi respectively according to molar content
2O
3, 0.5 ~ 3.0mol%Cr
2O
3, be added into pure phase barium carbonate powder piece and form full batching;
Step 4: getting full batching, zirconium ballstone and deionized water that step 3 obtains respectively, is to carry out ball milling, oven dry, granulation successively after mixing at 1: 1: 1 according to mass ratio, sieves, and forms the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2 ~ 4 hours when being warming up to 1300 ~ 1350 ℃ with 5 ℃/min, afterwards, cool to room temperature with the furnace after being cooled to 500 ℃ with 5 ℃/min;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain barium titanate-based lead-free relaxation ferroelectric ceramic material sample.
As preferred embodiment of the present invention, in the described step 4, the ball milling time is 4 hours.
As preferred embodiment of the present invention, in the described step 4, form the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, be that 4 ~ 8% tackiness agent is added into and wherein carries out granulation with mass concentration, 8 ~ 10% of binder constitutes oven dry material quality, sieve to crossing 40 orders and 80 mesh sieves respectively, material forms the granulation material in the middle of getting then.
As preferred embodiment of the present invention, tackiness agent is elected polyvinyl alcohol water solution as in the described step 4.
As preferred embodiment of the present invention, Bi
2O
3And Cr
2O
3Mol ratio be 1: 1.
A kind of barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material, its major ingredient is BaCO
3And TiO
2, its mol ratio is 1: (0.9 ~ 0.99), the material that mixes is Bi
2O
3And Cr
2O
3, wherein, according to molar percentage meter, Bi
2O
3All account for 0.5 ~ 3.0mol% of major ingredient with Cr2O3, simultaneously Bi
2O
3And Cr
2O
3Ratio is 1: 1.
A kind of barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material, its chemical formula is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=(0.01 ~ 0.06 wherein).
As preferred embodiment of the present invention, x=y=0.01,0.02,0.03,0.04,0.05 or 0.06.
As preferred embodiment of the present invention, x=y=0.06.
With respect to prior art, barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods of the present invention has the following advantages at least: 1. adopt the conventional solid-state method preparation, technical maturity is fit to industrialization production.2. adopt bismuth oxide and chromic oxide to carry out codoped, realize that the electricity price compensation is conducive to realize the disperse phase transformation of barium titanate ceramics.3. the non-plumbum ferroelectric stupalith of the inventive method preparation has tangible relaxation phenomena, becomes the double technically and economically excellent important candidate material of laminated ceramic capacitor to substituting the lead based relaxor ferroelectrics.
[description of drawings]
Fig. 1 is (Ba
0.94Bi
0.06) (Ti
0.94Cr
0.06) O
3The XRD figure spectrum of stupalith;
Fig. 2 is (Ba under the different frequency
0.94Bi
0.06) (Ti
0.94Cr
0.06) O
3The ceramic dielectric constant varies with temperature collection of illustrative plates.
[embodiment]
BaTiO of the present invention
3The unleaded bismuth-containing relaxation ferroelectric ceramic preparation methods of base, specific as follows:
Embodiment 1:
BaTiO in the present embodiment
3The chemical formula of the unleaded bismuth-containing relaxation ferroelectric ceramic material of base is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=0.01 wherein;
Step 1: be 1 according to mol ratio: (0.9 ~ 0.99) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after mixing at 1: 1: 1 after, place retort furnace to form the pure phase barium carbonate powder in 2 hours 1000 ~ 1150 ℃ of insulations, standby;
Step 3: be 1mol in the pure phase barium carbonate powder, take by weighing 0.5mol%Bi respectively according to molar content
2O
3, 0.5mol%Cr
2O
3, be added into the pure phase barium carbonate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively, be to mix at 1: 1: 1 according to mass ratio, ball milling is dried to such an extent that oven dry is expected after 4 hours, be that 4 ~ 8% polyvinyl alcohol water solution is added into and wherein carries out granulation with mass concentration, polyvinyl alcohol water solution accounts for 8 ~ 10% granulations of oven dry material quality, cross 40 orders and 80 mesh sieves and get middle material, form the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2 ~ 4 hours when being warming up to 1300 ~ 1350 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO
3The unleaded relaxation ferroelectric ceramic material sample of base.
Embodiment 2:
The chemical formula of the unleaded bismuth-containing relaxation ferroelectric ceramic material of present embodiment BaTiO3 base is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=0.02 wherein;
Step 1: be 1 according to mol ratio: (0.9 ~ 0.99) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after mixing at 1: 1: 1 after, place retort furnace to form the pure phase barium carbonate powder in 2 hours 1000 ~ 1150 ℃ of insulations, standby;
Step 3: be 1mol in the pure phase barium carbonate powder, take by weighing 1.0mol%Bi respectively according to molar content
2O
3, 1.0mol%Cr
2O
3, be added into the pure phase barium carbonate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively, be to mix at 1: 1: 1 according to mass ratio, ball milling is dried to such an extent that oven dry is expected after 4 hours, be that 4 ~ 8% polyvinyl alcohol water solution is added into and wherein carries out granulation with mass concentration, polyvinyl alcohol water solution accounts for 8 ~ 10% granulations of oven dry material quality, cross 40 orders and 80 mesh sieves and get middle material, form the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2 ~ 4 hours when being warming up to 1300 ~ 1350 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO
3The unleaded relaxation ferroelectric ceramic material sample of base.
Embodiment 3:
The chemical formula of the unleaded bismuth-containing relaxation ferroelectric ceramic material of present embodiment BaTiO3 base is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=0.03 wherein;
Step 1: be 1 according to mol ratio: (0.9 ~ 0.99) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after mixing at 1: 1: 1 after, place retort furnace to form the pure phase barium carbonate powder in 2 hours 1000 ~ 1150 ℃ of insulations, standby;
Step 3: be 1mol in the pure phase barium carbonate powder, take by weighing 1.5mol%Bi respectively according to molar content
2O
3, 1.5mol%Cr
2O
3, be added into the pure phase barium carbonate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively, be to mix at 1: 1: 1 according to mass ratio, ball milling is dried to such an extent that oven dry is expected after 4 hours, be that 4 ~ 8% polyvinyl alcohol water solution is added into and wherein carries out granulation with mass concentration, polyvinyl alcohol water solution accounts for 8 ~ 10% granulations of oven dry material quality, cross 40 orders and 80 mesh sieves and get middle material, form the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2 ~ 4 hours when being warming up to 1300 ~ 1350 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO
3The unleaded relaxation ferroelectric ceramic material sample of base.
Embodiment 4:
Present embodiment BaTiO
3The chemical formula of the unleaded bismuth-containing relaxation ferroelectric ceramic material of base is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=0.04 wherein;
Step 1: be 1 according to mol ratio: (0.9 ~ 0.99) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after mixing at 1: 1: 1 after, place retort furnace to form the pure phase barium carbonate powder in 2 hours 1000 ~ 1150 ℃ of insulations, standby;
Step 3: be 1mol in the pure phase barium carbonate powder, take by weighing 2.0mol%Bi respectively according to molar content
2O
3, 2.0mol%Cr
2O
3, be added into the pure phase barium carbonate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively, be to mix at 1: 1: 1 according to mass ratio, ball milling is dried to such an extent that oven dry is expected after 4 hours, be that 4 ~ 8% polyvinyl alcohol water solution is added into and wherein carries out granulation with mass concentration, polyvinyl alcohol water solution accounts for 8 ~ 10% granulations of oven dry material quality, cross 40 orders and 80 mesh sieves and get middle material, form the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2 ~ 4 hours when being warming up to 1300 ~ 1350 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO
3The unleaded relaxation ferroelectric ceramic material sample of base.
Embodiment 5:
Present embodiment BaTiO
3The chemical formula of the unleaded bismuth-containing relaxation ferroelectric ceramic material of base is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=0.05 wherein;
Step 1: be 1 according to mol ratio: (0.9 ~ 0.99) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after mixing at 1: 1: 1 after, place retort furnace to form the pure phase barium carbonate powder in 2 hours 1000 ~ 1150 ℃ of insulations, standby;
Step 3: be 1mol in the pure phase barium carbonate powder, take by weighing 2.5mol%Bi respectively according to molar content
2O
3, 2.0mol%Cr
2O
3, be added into the pure phase barium carbonate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively, be to mix at 1: 1: 1 according to mass ratio, ball milling is dried to such an extent that oven dry is expected after 4 hours, be that 4 ~ 8% polyvinyl alcohol water solution is added into and wherein carries out granulation with mass concentration, polyvinyl alcohol water solution accounts for 8 ~ 10% granulations of oven dry material quality, cross 40 orders and 80 mesh sieves and get middle material, form the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2 ~ 4 hours when being warming up to 1300 ~ 1350 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO
3The unleaded relaxation ferroelectric ceramic material sample of base.
Embodiment 6:
Present embodiment BaTiO
3The chemical formula of the unleaded bismuth-containing relaxation ferroelectric ceramic material of base is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=0.06 wherein;
Step 1: be 1 according to mol ratio: (0.9 ~ 0.99) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after mixing at 1: 1: 1 after, place retort furnace to form the pure phase barium carbonate powder in 2 hours 1000 ~ 1150 ℃ of insulations, standby;
Step 3: be 1mol in the pure phase barium carbonate powder, take by weighing 3.0mol%Bi respectively according to molar content
2O
3, 3.0mol%Cr
2O
3, be added into the pure phase barium carbonate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively, be to mix at 1: 1: 1 according to mass ratio, ball milling is dried to such an extent that oven dry is expected after 4 hours, be that 4 ~ 8% polyvinyl alcohol water solution is added into and wherein carries out granulation with mass concentration, polyvinyl alcohol water solution accounts for 8 ~ 10% granulations of oven dry material quality, cross 40 orders and 80 mesh sieves and get middle material, form the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2 ~ 4 hours when being warming up to 1300 ~ 1350 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO
3The unleaded relaxation ferroelectric ceramic material sample of base.
See also shown in Figure 1 and shown in Figure 2, (the Ba that embodiment 6 is prepared
0.94Bi
0.06) (Ti
0.94Cr
0.06) O
3In the XRD figure of the stupalith spectrum as can be seen, Bi among this embodiment
2O
3And Cr
2O
3All solid solution has formed the sosoloid shown in chemical formula.Simultaneously, Fig. 2 medium dielectric constant microwave medium peak not only flattens smooth but also has frequency dispersion, and namely with the increase of frequency, the corresponding temperature of specific inductivity maximum value lock is offset to the high temperature direction.This specific inductivity peak flattens and phenomenon with frequency dispersion is relaxation phenomena.This is because Bi ionic replacement Ba position and Cr ionic replacement Ti position form the electricity price compensation, simultaneously, forms the fluctuating of micro components.The composition fluctuation theory is based on the proposition of compound ion stochastic distribution phenomenon.Think that different ions such as occupies at random at isomorphous position, produce the microscopic concentration microcell different with integral macroscopic concentration, form different microcell and have slightly different Curie temperature, the transition temperature area of generation broadening on the macroscopic view.Even think that the average component of microcell is identical, also may form the different microcell of structure owing to cell configuration is different, thereby produce the disperse phase transformation.The barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material of the inventive method preparation has tangible relaxation phenomena, becomes the double technically and economically excellent important candidate material of laminated ceramic capacitor to substituting the lead based relaxor ferroelectrics.
Claims (9)
1. barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods is characterized in that: may further comprise the steps:
Step 1: be 1:(0.9～0.99 according to mol ratio) takes by weighing BaCO
3And TiO
2Mix and form mixture A;
Step 2: get mixture A, zirconium ballstone and deionized water respectively, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place retort furnace to form the pure phase barium carbonate powder in 2 hours 1000～1150 ℃ of insulations, standby;
Step 3: be 1mol in the pure phase barium carbonate powder, take by weighing 0.5～3.0mol%Bi respectively according to molar content
2O
3, 0.5～3.0mol%Cr
2O
3, be added into the pure phase barium carbonate powder and form full batching;
Step 4: getting full batching, zirconium ballstone and deionized water that step 3 obtains respectively, is to carry out ball milling, oven dry, granulation successively after 1:1:1 mixes according to mass ratio, sieves, and forms the granulation material;
Step 5: step 4 gained granulation material is made sample under the pressure of 120MPa, then, place with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 2～4 hours when being warming up to 1300～1350 ℃ with 5 ℃/min, afterwards, cool to room temperature with the furnace after being cooled to 500 ℃ with 5 ℃/min;
Step 6: behind polishing, the sample that sinters of cleaning step five, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material.
2. barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods as claimed in claim 1, it is characterized in that: in the step 4, the ball milling time is 4 hours.
3. barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods as claimed in claim 1, it is characterized in that: in the step 4, form the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, be that 4～8% tackiness agent is added into and wherein carries out granulation with mass concentration, 8～10% of binder constitutes oven dry material quality, sieve to crossing 40 orders and 80 mesh sieves respectively, material forms the granulation material in the middle of getting then.
4. barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods as claimed in claim 3, it is characterized in that: described tackiness agent is elected polyvinyl alcohol water solution as.
5. barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods as claimed in claim 1 is characterized in that: Bi
2O
3And Cr
2O
3Mol ratio be 1:1.
6. as any one the described barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods in the claim 1 to 5, it is characterized in that: the major ingredient of prepared barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material is BaCO
3And TiO
2, its mol ratio is 1:(0.9～0.99), the material that mixes is Bi
2O
3And Cr
2O
3, wherein, according to molar percentage meter, Bi
2O
3And Cr
2O
3All account for 0.5～3.0mol% of major ingredient, simultaneously Bi
2O
3And Cr
2O
3Ratio is 1:1.
7. as any one the described barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods in the claim 1 to 5, it is characterized in that: the chemical formula of prepared barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material is (Ba
1-xBi
x) (Ti
1-yCr
y) O
3, x=y=(0.01～0.06 wherein).
8. barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods according to claim 7 is characterized in that: x=y=0.01,0.02,0.03,0.04,0.05 or 0.06.
9. barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic preparation methods according to claim 7 is characterized in that: x=y=0.06.
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| CN105130424A (en) * | 2015-08-24 | 2015-12-09 | 陕西科技大学 | BiYO3-doped BaTiO3-based relaxor ferroelectric and preparation method therefor |
| CN105236958A (en) * | 2015-08-24 | 2016-01-13 | 陕西科技大学 | X9R type multilayer ceramic capacitor dielectric material and preparation method therefor |
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| CN114671681B (en) * | 2022-04-11 | 2023-04-11 | 北京科技大学 | Barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and preparation method thereof |
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Effective date of registration: 20201224 Address after: 224000 Qingyang Road (within Qingdun Office), Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (8) Patentee after: Yancheng Qinglong Jinbang water Co.,Ltd. Address before: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Pengbo Information Technology Co.,Ltd. Effective date of registration: 20201224 Address after: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Pengbo Information Technology Co.,Ltd. Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
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Correction item: Patentee|Address Correct: Yancheng Qingdun Jinbang Water Co., Ltd.|224000 Qingyang Road, Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (in Qingdun Office) (8) False: Yancheng Qingyi Jinbang Water Co., Ltd.|224000 Qingyang Road, Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (in Qingdun Office) (8) Number: 02-01 Volume: 37 |
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Granted publication date: 20131009 |