CN102674832A - 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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- CN102674832A CN102674832A CN2012101494527A CN201210149452A CN102674832A CN 102674832 A CN102674832 A CN 102674832A CN 2012101494527 A CN2012101494527 A CN 2012101494527A CN 201210149452 A CN201210149452 A CN 201210149452A CN 102674832 A CN102674832 A CN 102674832A
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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
3Unleaded bismuth-containing relaxation ferroelectric ceramic material of base and preparation method.
[background technology]
Relaxation ferroelectric ceramic is one type of noticeable material of ten minutes 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 issued 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 one type of ferroelectric ceramic(s) with 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 Tc, 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 extensive studies.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 showing that this system meets existing theoretical model with the correlation theory 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 through 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 realizing above-mentioned purpose, 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: according to mol ratio is 1: (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 titanate powder piece in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder piece is 1mol, takes 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 titanate 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 processed sample under the pressure of 120MPa; Then; Placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is warming up to 500 ℃ of insulation 60min with 2 ℃/min, and 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,,, obtain barium titanate-based lead-free relaxation ferroelectric ceramic material sample in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides.
As preferred embodiment of the present invention, in the said step 4, the ball milling time is 4 hours.
As preferred embodiment of the present invention; In the said step 4; Forming the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, is that 4 ~ 8% tackiness agent is added into and wherein carries out granulation, 8 ~ 10% of binder constitutes oven dry material quality with mass concentration; 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 said 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 helps realizing 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 is with the temperature variation 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: according to mol ratio is 1: (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 titanate powder in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder is 1mol, takes by weighing 0.5mol%Bi respectively according to molar content
2O
3, 0.5mol%Cr
2O
3, be added into pure phase barium titanate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively; According to mass ratio is mixing in 1: 1: 1; Ball milling dry after 4 hours oven dry material, 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 processed sample under the pressure of 120MPa; Then, placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is 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,,, obtain BaTiO in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides
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: according to mol ratio is 1: (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 titanate powder in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder is 1mol, takes by weighing 1.0mol%Bi respectively according to molar content
2O
3, 1.0mol%Cr
2O
3, be added into pure phase barium titanate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively; According to mass ratio is mixing in 1: 1: 1; Ball milling dry after 4 hours oven dry material, 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 processed sample under the pressure of 120MPa; Then, placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is 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,,, obtain BaTiO in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides
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: according to mol ratio is 1: (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 titanate powder in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder is 1mol, takes by weighing 1.5mol%Bi respectively according to molar content
2O
3, 1.5mol%Cr
2O
3, be added into pure phase barium titanate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively; According to mass ratio is mixing in 1: 1: 1; Ball milling dry after 4 hours oven dry material, 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 processed sample under the pressure of 120MPa; Then, placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is 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,,, obtain BaTiO in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides
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: according to mol ratio is 1: (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 titanate powder in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder is 1mol, takes by weighing 2.0mol%Bi respectively according to molar content
2O
3, 2.0mol%Cr
2O
3, be added into pure phase barium titanate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively; According to mass ratio is mixing in 1: 1: 1; Ball milling dry after 4 hours oven dry material, 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 processed sample under the pressure of 120MPa; Then, placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is 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,,, obtain BaTiO in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides
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: according to mol ratio is 1: (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 titanate powder in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder is 1mol, takes by weighing 2.5mol%Bi respectively according to molar content
2O
3, 2.0mol%Cr
2O
3, be added into pure phase barium titanate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively; According to mass ratio is mixing in 1: 1: 1; Ball milling dry after 4 hours oven dry material, 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 processed sample under the pressure of 120MPa; Then, placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is 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,,, obtain BaTiO in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides
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: according to mol ratio is 1: (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 titanate powder in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder is 1mol, takes by weighing 3.0mol%Bi respectively according to molar content
2O
3, 3.0mol%Cr
2O
3, be added into pure phase barium titanate powder and form full batching;
Step 4: get full batching, zirconium ballstone and deionized water that step 3 obtains respectively; According to mass ratio is mixing in 1: 1: 1; Ball milling dry after 4 hours oven dry material, 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 processed sample under the pressure of 120MPa; Then, placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is 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,,, obtain BaTiO in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides
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
3Can find out Bi among this embodiment in the XRD figure spectrum of stupalith
2O
3And Cr
2O
3All solid solution has formed the sosoloid shown in chemical formula.Simultaneously, Fig. 2 medium dielectric constant microwave medium peak is flattened but also have frequency dispersion not only, and promptly with the increase of frequency, the corresponding temperature of specific inductivity peak lock squints 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 microscopic concentration and the different microcell of integral macroscopic concentration, form different microcell and have slightly different Tc, the transition temperature area of wideization of generation on the macroscopic view.Even think that the average component of microcell is identical, also possibly form the different microcell of structure, thereby produce the disperse phase transformation owing to cell configuration is different.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: according to mol ratio is 1: (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 titanate powder in 2 hours 1000 ~ 1150 ℃ of insulations, subsequent use;
Step 3: in pure phase barium titanate powder is 1mol, takes 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 titanate 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 mixing at 1: 1: 1 according to mass ratio, sieves, and forms the granulation material;
Step 5: step 4 gained granulation material is processed sample under the pressure of 120MPa; Then; Placing with the zirconium white is in the inherent high temperature box furnace of aluminum oxide saggar of backing plate, is warming up to 500 ℃ of insulation 60min with 2 ℃/min, and 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,,, obtain barium titanate-based lead-free relaxation ferroelectric ceramic material sample in 600 ℃ of sintering 20 minutes at the even coated silver electrode slurry of sample tow sides.
2. barium titanate-based lead-free relaxation ferroelectric ceramic preparation methods as claimed in claim 1 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; Forming the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, is that 4 ~ 8% tackiness agent is added into and wherein carries out granulation, 8 ~ 10% of binder constitutes oven dry material quality with mass concentration; 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: said 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. prepare the barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material of gained according to any one the described preparation method in the claim 1 to 5, it is characterized in that: 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
3And Cr
2O
3All account for 0.5 ~ 3.0mol% of major ingredient, simultaneously Bi
2O
3And Cr
2O
3Ratio is 1: 1.
7. prepare the barium titanate-based lead-free bismuth-containing relaxation ferroelectric ceramic material of gained according to each described preparation method in the claim 1 to 5, it is characterized in that: its chemical formula 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 material 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 material according to claim 7 is characterized in that: x=y=0.06.
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| CN109206135A (en) * | 2018-09-28 | 2019-01-15 | 华中科技大学 | A kind of thermal sensitive ceramic material and preparation method thereof with high-temperature coefficient |
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| CN109206135A (en) * | 2018-09-28 | 2019-01-15 | 华中科技大学 | A kind of thermal sensitive ceramic material and preparation method thereof with high-temperature coefficient |
| CN109206135B (en) * | 2018-09-28 | 2020-05-19 | 华中科技大学 | Thermal sensitive ceramic material with high temperature coefficient and preparation method thereof |
| CN114671681A (en) * | 2022-04-11 | 2022-06-28 | 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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