CN105152647A - Sintering temperature-sensitive bismuth titanate-based lead-free dielectric ceramic material - Google Patents
Sintering temperature-sensitive bismuth titanate-based lead-free dielectric ceramic material Download PDFInfo
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- CN105152647A CN105152647A CN201510400091.2A CN201510400091A CN105152647A CN 105152647 A CN105152647 A CN 105152647A CN 201510400091 A CN201510400091 A CN 201510400091A CN 105152647 A CN105152647 A CN 105152647A
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Abstract
The present invention discloses preparation and electrical property characterization of a sintering temperature-sensitive bismuth titanate-based lead-free dielectric ceramic material, wherein the chemical general formula of the ceramic is Bi4Ti3O12, primary pre-burning is performed at a temperature of 800 DEG C by using a traditional solid-phase method, and sintering is performed at two different temperatures such as 1100 DEG C and 1150 DEG C. According to the present invention, the Curie temperature is 663 DEG C when the sintering temperature is 1100 DEG C, the relative dielectric constant close to the Curie temperature achieves more than or equal to 76.7, while the Curie temperature is 656 DEG C when the sintering temperature is 1150 DEG C, the relative minimum dielectric constant close to the Curie temperature can achieve 22.67, such that the preferred ceramic sheet achieving the relative dielectric constant of more than or equal to 76.7 has the small dielectric loss; the activation energy of the prepared ceramic sheet is 0.50-0.73 through electric mode coefficient calculation; and when the sintering temperature is only increased by 50 DEG C, the significant changes are generated in the value and the change trends of the dielectric constant, the dielectric loss and the like of the material.
Description
Technical field
The invention belongs to electronic ceramic component preparing technical field, particularly a kind of bismuth titanate based unleaded dielectric ceramic to sintering temperature sensitivity, it is the dielectric materials of uhligite laminate structure of a kind of new high dielectric constant, low-dielectric loss, change sintering temperature a little, specific inductivity, the dielectric loss and activation energy etc. of this pottery there occurs obvious change.
Background technology
Along with going deep into of ferroelectric memory material research, bismuth-containing layer perovskite ferroelectric materials (bismuthlayer-structuredferroelectric:BLSF) causes the great interest of people, and the general formula of BLSF can be expressed as: (Bi
2o
2)
2+(A
m-1b
mo
3m+1)
2-(m can get 6 from 1).Wherein bismuth titanates (Bi
4ti
3o
12be called for short BIT) be typically bismuth laminated ferroelectric material, there is lower treatment temp, higher Curie temperature (Tc), good remnant polarization, higher specific inductivity, low dielectric loss, preferably ferroelectric and piezoelectric property, fatigue resistance and the advantage such as not leaded, becoming one of novel memory devices candidate material, is also the focus of current BLSF investigation of materials.It has good ferroelectric properties, is expected to most become manufacture one of Nonvolatile ferroelectric memory material, no matter is in industrial or agricultural, national defence, scientific research, still in daily life, all has a wide range of applications.Simultaneously, the electricity of its uniqueness, optics, photoelectronics performance, also have broad application prospects in modern microelectronic, MEMS (micro electro mechanical system), information storage etc., it has good photocatalytic under visible light makes its large-scale application become possibility in Treatment of Industrial Water.
But, along with the development of science and technology, the requirement of people to the performance of BIT material is more and more higher, although made significant headway to the research of BIT ferroelectric material, but research still shows that BIT material also exists that densified sintering product is poor, piezoelectric activity is low, coercive field Ec is large, be unfavorable for the deficiencies such as polarization, cause its piezoelectric property lower, therefore can not be satisfied with industry and commerce development completely to the demand of its more high-quality.Because BIT has had stronger piezoelectricity and ferroelectric properties, so this time we mainly study the factor affecting its dielectric characteristics.Test by changing sintering temperature, and then affect its microtexture, prepare high dielectric property, low-loss novel information material, allowing BIT be better Institute of Science use, is better mankind's service.
Summary of the invention
The object of this invention is to provide a kind of bismuth titanate based unleaded dielectric ceramic material to sintering temperature sensitivity, its chemical general formula is: Bi
4ti
3o
12.It is high that prepared ceramic phase has specific inductivity for other leadless piezoelectric ceramics, and dielectric loss is little, and resistivity is large, to features such as sintering temperature are responsive.
For reaching goal of the invention, the invention provides the preparation method of unleaded dielectric ceramic, its method comprises the following steps:
(1) reactant is TiO
2and Bi
2o
3(purity is 99%, uses highly purified reactant can reduce the impact of impurity on reaction result), is measured by chemical general formula after reactant is cooled to room temperature in moisture eliminator and obtains than weighing, and sample is by traditional solid phase method processing preparation.Concrete formula is as follows:
| Raw material | Bi 2O 3 | TiO 2 |
| Consumption (g) | 7.9545 | 2.0455 |
(2) powder mixes and carries out 24 hours ball millings and drying with stable zirconium oxide abrasive thing in Virahol.Be 800 DEG C of pre-burnings by the powder of drying in temperature, the time is 2 hours, after pre-burning, by powder ball milling 12 hours, then by this coccoid grinding granulating and forming.
(3) be pressed into disk green sheet, concrete dimension reference embodiment by above-mentioned granular solid single shaft Die cast machine, and under 200 MPa pressure isostatic cool pressing.Then sample average is divided into two portions, is respectively charged into two closed alumina crucibles, to reduce the loss of volatile oxidation bismuth as far as possible, one sinters 2-3 hour at the temperature of 1100 DEG C, and another sinters 2-3 hour at the temperature of 1150 DEG C.It is probe into Bi that sintering temperature is improved 50 DEG C by this experiment
4ti
3o
12the key of dielectric properties.
(4) a ceramic plate part being ground to powder, is single-phase through X-ray diffraction analysis.
(5) the ceramic plate grinding and polishing calcined by another part carries out Dielectric measuring to the thickness of 0.9mm.Bronze is applied to tow sides, in 800 DEG C of stoves, is fired into electrode, and carry out the measurement of high temperature impedance spectrum in the threaded pipe type stove of non-conductive; IS data are corrected by the geometrical shape (thickness/area of particle) of sample, and use ZView software to analyze.Relative permittivity and dielectric loss are tested at 20 DEG C ~ 600 DEG C by electric impedance analyzer.
Sintering temperature is 1100 DEG C of Curie temperatures 663 DEG C after testing, now reach more than 76.7 at the relative permittivity of vicinity of Curie temperatures, sintering temperature is 1150 DEG C of Curie temperatures is 656 DEG C, relative permittivity reaches more than 22.67, and when this shows 1100 DEG C, the dielectric properties of ceramic plate sample are obviously better than 1150 DEG C.
(6) cross-section structure of Electronic Speculum to ceramic plate is used to study.Polishing is carried out in ceramic plate cross section, 990 DEG C of thermal etchings 11 hours, then with gold coating.And use mini-probe to carry out electron probe microanalysis under 20 kilovoltages in random 12 groups of regions selected.
(7) cross-section structure of Electronic Speculum to ceramic plate is used to study and microanalysis.
The present invention has following characteristics:
(1) traditional solid-phase sintering method is adopted, by raw material TiO
2and Bi
2o
3according to stoichiometric.Successfully synthesize BIT type material.
(2) the present invention by carrying out sintering the ceramic plate obtaining different dielectric characteristic under 1040 DEG C ~ 1180 DEG C differing tempss, for probe into different chemical reaction under temperature on the impact of material property, choose reverse two distinct temperature points of (1150 DEG C) of best performance (1100 DEG C) and performance and carry out detailed analysis, and then filter out the dielectric materials of the most realistic application, achieve the improvement to the unleaded dielectric ceramic properties of BIT.
(3) the present invention is after being theoretical material by XRD diffraction analysis confirmation experiment material, high temperature Impedance Analysis is carried out in electric impedance analyzer, obtain relative permittivity value and the dielectric loss numerical value of material, and analyze with Zview software, obtain each side electric property data of related ceramic material, significant reference value.
(4) the present invention carries out Impedance Analysis take off data display material at the following tool high-k of Curie temperature and low-dielectric loss, log (σ/ohm
-1cm
-1) VS1000/T curve shows that the activation energy of material is between 0.50 and 0.73.
In a word, the ceramic dielectric constant prepared by the inventive method is large, and dielectric loss is little and responsive to sintering temperature, can change the electric property of pottery by changing sintering temperature.
Accompanying drawing explanation
Fig. 1 is XRD diffracting spectrum, and diffraction analysis shows that experiment reaction gained ceramic plate is single-phase, consistent with theoretical material;
Fig. 2 represents that material is 800 DEG C of pre-burnings, and at 1100 DEG C, the measured relative permittivity of sintering is with temperature variation curve residing for material environment;
Fig. 3 represents that material is 800 DEG C of pre-burnings, and at 1150 DEG C, the measured relative permittivity of sintering is with temperature variation curve residing for material environment;
Fig. 4 represents that material is 800 DEG C of pre-burnings, and at 1100 DEG C, the measured Loss tangent of sintering is with temperature variation curve residing for material environment;
Fig. 5 represents that material is 800 DEG C of pre-burnings, and at 1150 DEG C, the measured Loss tangent of sintering is with temperature variation curve residing for material environment;
Fig. 6 represents that two groups of material log (σ/ohm-1cm-1) change fit line (slope represents activation energy size) with 1000/T;
Fig. 7 represents that material is 800 DEG C of pre-burnings, the measured Electronic Speculum figure of sintering at 1100 DEG C;
Fig. 8 represents that material is 800 DEG C of pre-burnings, the measured Electronic Speculum figure of sintering at 1150 DEG C.
Embodiment
Below by by the more detailed explanation the present invention of embodiment, but following examples are only illustrative, and protection scope of the present invention is by the restriction of these embodiments.
Embodiment one: prepared by piezoelectric ceramics
Chemical equation: 3TiO
2+ 2Bi
2o
3→ Bi
4ti
3o
12
Adopt TiO
2and Bi
2o
3two kinds of raw material powders, weigh by chemical general formula, reactant is cooled to room temperature in moisture eliminator, carries out drying and processing, gets TiO
2quality 2.0455g, Bi
2o
3quality is 7.9545g, and sample is by traditional solid phase method processing preparation.Concrete steps are as follows: mixed in Virahol by powder and carry out 24 hours ball millings and drying with stable zirconium oxide abrasive thing.By the powder of drying 800 DEG C of pre-burnings, time is 2 hours, after pre-burning, by powder ball milling 12 hours, then this coccoid is ground again again and is configured as granular, and in blocks with the single shaft steel mold pressing of green compact, (area is 0.6951cm to be pressed into disk size, diameter is 0.941cm, and thickness is 0.168cm), and under 200 MPa pressure isostatic cool pressing.Then sample is loaded the alumina crucible closed, at 1100 DEG C, sinter 2-3 hour, obtain the ceramic plate sintered, sample number into spectrum is a.
Step is the same with above-mentioned, 800 DEG C of pre-burnings, and the time is 2 hours, at 1150 DEG C, sinter 2-3 hour, and sample number into spectrum is b.
Embodiment two: the Dielectric measurement of piezoceramic material sample
(1) Fig. 1 is XRD diffracting spectrum, shows that experiment reaction gained ceramic plate is single-phase through diffraction analysis, consistent with theoretical material.
(2) relative permittivity is measured
Fig. 2 represents, sample a pre-burning at 800 DEG C, and at 1100 DEG C, the measured relative permittivity of calcining is with variation of ambient temperature curve residing for sample, and relative permittivity comparatively fast rises, at Curie temperature T when the following lesser temps of Curie temperature
csuddenly increase near=663 DEG C, under 100kHz, 250kHz and 1MHz tri-kinds of different frequencies, the peak value of r reaches 205.4,131.6 and 76.7, Tc respectively and sharply declines later.By comparative data, can find that frequency is higher, relative permittivity is less.
Fig. 3 represents, sample b is 800 DEG C of pre-burnings, and at 1150 DEG C, relative permittivity measured by sintered ceramic sheet is with variation of ambient temperature curve residing for sample.It is similar to Fig. 2 that relative permittivity varies with temperature general trend, slowly increased before this, at Curie temperature T
cslightly fast growth near=656 DEG C, 100kHz, 250kHz and 1MHz tri-kinds of different frequencies reach 49.61,34.70 and 22.67 respectively at the peak value of near Curie temperature r, and dielectric constant values has the trend reduced a little afterwards.With sample when sintering for 1100 DEG C compared with the data obtained, its specific inductivity obviously reduces, and illustrates that the rising of sintering temperature can cause the decline of dielectric material performance.
Curie temperature (T under different condition
c) place's dielectric constant values is in table one
Curie temperature place relative permittivity value when table one sintering temperature is different
(3) dielectric loss take off data
Fig. 4 represents, a sample sinters tg δ and varies with temperature curve at 1100 DEG C of temperature, and 150 DEG C of internal loss tangent angles are almost 0, negligible, and slowly growth declines again subsequently.By comparative data, can find that frequency is higher, dielectric loss is less.
Fig. 5 represents, b sample sinters tg δ and varies with temperature curve at 1150 DEG C of temperature
Sinter at 1150 DEG C of temperature, have relative to sintering temperature and low loss angle and rise by a relatively large margin, trend constantly rises generally, larger on dielectric properties impact.
Under different condition, Curie temperature place dielectric loss value is in table two.
Curie temperature place dielectric loss value when table two sintering temperature is different
(4) log (σ/ohm-1cm-1) VS1000/T activation energy and Z* impedance chart take off data
Fig. 6 represents, the log (σ/ohm-1cm-1) of two samples changes fit line (slope represents activation energy size) with 1000/T.
Show Ea by upper figure and be all greater than 0.5, activation energy is between 0.50 and 0.73.Ceramics sample under two kinds of sintering temperatures is good insulating material.
(5) microtexture measurement and analysis
Fig. 7 and Fig. 8 result shows, sample grain-size 1100 DEG C time is significantly less than 1150 DEG C, and distribution uniform.
Claims (3)
1., to a bismuth titanate based unleaded dielectric ceramic material for sintering temperature sensitivity, it is characterized in that chemical general formula is: Bi
4ti
3o
12, through 800 DEG C of pre-burnings, 1100 DEG C of sintering form, and relative permittivity reaches more than 76.7.
2., to a bismuth titanate based unleaded dielectric ceramic material for sintering temperature sensitivity, it is characterized in that chemical general formula is: Bi
4ti
3o
12through 800 DEG C of pre-burnings, 1150 DEG C of sintering form, and relative permittivity reaches more than 22.67.
3., to a preparation method for the bismuth titanate based unleaded dielectric ceramic material of sintering temperature sensitivity, it is characterized in that step is:
(1) selection purity is the reactant TiO of 99%
2and Bi
2o
3, reactant is cooled to room temperature in moisture eliminator, is then measured than weighing by chemical general formula;
(2) powder mixes and carries out 24 hours ball millings and drying with stable zirconium oxide abrasive ball in Virahol.By the powder of drying 800 DEG C of pre-burnings, the time is 2 hours, after each pre-burning, by powder ball milling 12 hours, is more again again ground by this coccoid and is configured as granular;
(3) above-mentioned granular solid is pressed into disk green sheet, and under 200 MPa pressure isostatic cool pressing, sample is divided into two portions, and a part of sample loads the alumina crucible closed, to reduce the loss of volatile oxidation bismuth as far as possible, at 1100 DEG C of sintering 2-3 hour; Another part sample loads the alumina crucible closed, to reduce the loss of volatile oxidation bismuth as far as possible, at 1150 DEG C of sintering 2-3 hour;
(4) test, a ceramic plate part is ground to powder, is single-phase by X-ray diffraction analysis;
Ceramic plate grinding and polishing to the thickness of 0.9mm of another part calcining carries out Dielectric measuring, and bronze is applied to contrary parallel surface, and coated sheet is fired into electrode in 800 DEG C of stoves, and carries out the measurement of high temperature impedance spectrum in the threaded pipe type stove of non-conductive; Relative permittivity and dielectric loss are tested at 20 DEG C ~ 600 DEG C by electric impedance analyzer;
(5) cross-section structure of Electronic Speculum to ceramic plate is used to study and microanalysis.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693238A (en) * | 2016-01-05 | 2016-06-22 | 湖北大学 | Sodium bismuth titanate based lead-free piezoelectric ferroelectric material with low dielectric property and low loss |
| CN115010493A (en) * | 2022-05-31 | 2022-09-06 | 清华大学 | High-entropy pyrochlore dielectric ceramic material and preparation method and application thereof |
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| CN104402433A (en) * | 2014-11-26 | 2015-03-11 | 陕西科技大学 | Preparation method for low-loss and high-resistivity Bi4Ti3O12-based lead-free piezoelectric ceramics |
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2015
- 2015-07-09 CN CN201510400091.2A patent/CN105152647A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104402433A (en) * | 2014-11-26 | 2015-03-11 | 陕西科技大学 | Preparation method for low-loss and high-resistivity Bi4Ti3O12-based lead-free piezoelectric ceramics |
Non-Patent Citations (2)
| Title |
|---|
| 艾桃桃: "Bi4Ti3O12陶瓷的制备及微观结构", 《中国陶瓷》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693238A (en) * | 2016-01-05 | 2016-06-22 | 湖北大学 | Sodium bismuth titanate based lead-free piezoelectric ferroelectric material with low dielectric property and low loss |
| CN115010493A (en) * | 2022-05-31 | 2022-09-06 | 清华大学 | High-entropy pyrochlore dielectric ceramic material and preparation method and application thereof |
| CN115010493B (en) * | 2022-05-31 | 2023-01-13 | 清华大学 | High-entropy pyrochlore dielectric ceramic material and preparation method and application thereof |
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Application publication date: 20151216 |