CN106242546A - A kind of Novel Room Temperature many ferrum pottery of high polarization intensity and preparation method thereof - Google Patents

A kind of Novel Room Temperature many ferrum pottery of high polarization intensity and preparation method thereof Download PDF

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CN106242546A
CN106242546A CN201610695661.XA CN201610695661A CN106242546A CN 106242546 A CN106242546 A CN 106242546A CN 201610695661 A CN201610695661 A CN 201610695661A CN 106242546 A CN106242546 A CN 106242546A
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room temperature
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ceramic
ferrum
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CN106242546B (en
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董显林
刘宁涛
梁瑞虹
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Shanghai Institute of Ceramics of CAS
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Abstract

Novel Room Temperature many ferrum pottery that the present invention relates to a kind of high polarization intensity and preparation method thereof, the chemical composition of described room temperature many ferrum ceramic material is: 0.75 ((1‑x)BiFeO3‑xBiGaO3)‑0.25Ba0.85Ca0.15Ti0.90Zr0.10O3+yMnCO3, wherein, 0 ＜x≤ 0.05, y≤0.5wt%.Being regulated and controled by component, obtained having the ferromagnetism of excellence and ferroelectric room temperature many ferrum ceramic material simultaneously, it has high remanent polarization (22 ~ 44 μ C/cm2), a kind of Novel Room Temperature many ferrum ceramic material of high ferromagnetic property (0.09 ~ 0.27emu/g).

Description

A kind of Novel Room Temperature many ferrum pottery of high polarization intensity and preparation method thereof
Technical field
The invention belongs to function ceramics field, relate to a kind of room temperature many ferrum ceramic material, particularly relate to a kind of ferrous acid bismuthino Many ferrum ceramic material and preparation method thereof.
Background technology
Multi-ferroic material refers to a kind of have the novel many of ferromagnetic, two kinds of ferroelectricity, ferrum bullet etc. and two or more character simultaneously Functional material, the magneto-electric coupled effectiveness that wherein magnetic, electricity cause in order can produce magnetic polarization and additional magnetic under extra electric field Producing electric polarization after the match, the design for information recording device provides an extra degree of freedom, and it is in novel sensor, spin The aspect such as electronic device and high-density memory device has broad application prospects.
BiFeO3(BFO) it is that at room temperature there is ferroelectricity and the anti-ferromagnetic multi-ferroic material of G type, there is high Curie Temperature Tc (1103K) and Ne&1&el temperature TN(643K), it is that minority has ferroelectricity and anti-ferromagnetism two kinds the most simultaneously One of many iron store of ordered structure.Owing to bismuth element is volatile and the problem such as ferrum element valence state easily fluctuation, bismuth ferrite Building-up process in generally along with Bi2Fe4O9And Bi25FeO40Deng the generation of the second phase, thus bismuth ferrite sample is caused to leak electricity Flow compared with big, resistivity is relatively low, dielectric constant is less, at room temperature hardly results in saturated ferroelectric hysteresis loop.
For BiFeO3The preparation of pottery, people are except using special preparation technology (spark plasma sintering, quick liquid Phase sintering etc.) outward, typically use modification by ion-doping or with other Perovskite Phase solid solutions, improve its performance.Chen et al. (Journal of Applied Physics, 105,054107 (2009)) is by BiFeO3Middle introducing NaNbO3(BFO-NN), Obtain remanent polarization (Pr) 1.30 μ C/cm2, remanent magnetization is (Mr) 0.14emu/g, and magnetic coercive field is Room temperature many ferrum pottery of 6.48kOe.Lin et al. (J.Am.Ceram.Soc., 97 [6] 1,809 1818 (2014)) is prepared for Sc and changes The BiFeO of property3–BaTiO3(BFO-BT-BS) ternary ceramics, it is thus achieved that bigger remanent polarization (Pr=19.1～20.4 μC/cm2), its remanent magnetization is 0.059emu/g, and magnetic coercive field is 2.51kOe.Kwok et al. (Ceramic International 40 (2014) 1335-1339) attempt at BiFeO3Middle introducing (BaCa) (TiZr) O3(BFO-BCZT), surplus Though remaining polarization intensity obtains certain raising, but ferromagnetism is not improved, and (Pr is about 24.5 μ C/cm2, Mr is about 0.00135emu/g).Therefore, ferromagnetic and ferroelectric properties mutually restricts, and cannot be improved, pole in same single_phase system simultaneously The big application limiting BFO Quito iron material.
Summary of the invention
For the problems referred to above, it is an object of the invention to provide a kind of room temperature many ferrum pottery with high remanent polarization Ceramic material and preparation method thereof, it has the multi-ferrum property of excellence, is expected in field application such as data storage, micro-electricity electronics.
On the one hand, the present invention provides a kind of room temperature many ferrum ceramic material, the chemical composition of described room temperature many ferrum ceramic material For:
0.75((1-x)BiFeO3-xBiGaO3)-0.25Ba0.85Ca0.15Ti0.90Zr0.10O3+yMnCO3, wherein, 0 ＜ x≤ 0.05, it is preferable that 0 ＜ x≤0.04, y≤0.5wt%, it is preferable that y=0.5wt%.
The present invention, based on ferroelectric properties excellent for BCZT, is firstly introduced BiGaO3, devise a new BFO-BG-BCZT Ternary system, is simultaneously introduced 0.5wt%MnCO3As additive, reduce system loss.Regulated and controled by component, obtained simultaneously Having the ferromagnetism of excellence and ferroelectric room temperature many ferrum ceramic material, it has high remanent polarization (22～44 μ C/ cm2), a kind of Novel Room Temperature many ferrum ceramic material of high ferromagnetic property (0.09～0.27emu/g).BFO-BG-BCZT ternary The multi-ferrum property of pottery excellence makes it have important using value in magneto-electric coupled technical field.
Preferably, 0 ＜ x≤0.04.In accordance with the invention it is possible to obtain room temperature many ferrum pottery material that multi-ferrum property is more excellent Material.
The remanent polarization maximum of the room temperature many ferrum ceramic material in the present invention can reach 43.86 μ C/cm2, and its After polarization processes, piezoelectric modulus can reach 90pC/N, and remanent magnetization can enough reach 0.27emu/g.
On the other hand, the present invention provides the preparation method of above-mentioned room temperature many ferrum ceramic material, comprises the steps:
A () solid phase method prepares ceramic powder, with Bi2O3、BaCO3、TiO2、ZrO2、CaCO3、MnCO3、Fe2O3、Ga2O3Powder body is Raw material, prepares according to the stoichiometric proportion of corresponding element, and ball milling mixes, and briquetting obtains ceramic powder after calcining；
B (), by the ceramic powder ball milling of step (a) gained, pelletize, molding, obtains ceramic body；
C () obtains described many ferrum ceramic material after being sintered by the ceramic body of step (b) gained.
The present invention prepares room temperature many ferrum ceramic material by conventional solid reaction method, and technique is simple, parameter is easily-controllable, low cost Honest and clean, it is easy to industrialized production.
It is preferred that in step (a), described ball milling is mixed into the mixing of wet ball-milling method, according to raw material: abrading-ball: ethanol=1: (1.8～2.2): the mass ratio of (0.7～1.0) mixes 23～25 hours, and wherein abrading-ball is steel ball, zirconium ball or agate ball；Described Calcining, for rise to 750～800 DEG C with the programming rate of 2～5 DEG C/min, is incubated 2～5 hours.
It is preferred that in step (b), described ball milling uses wet ball-milling method, according to ceramic powder: abrading-ball: ethanol=1: (1.8～2.2): the quality of (0.5～0.7) is than fine grinding, and wherein abrading-ball is steel ball, zirconium ball or agate ball；Described wet ball-milling method The fine grinding time is 23～25 hours, obtains ceramic powder after fine grinding.
It is preferred that in step (b), add binding agent pelletize, the addition of binding agent be ceramic powder weight 5～ 8wt.%, is aged 22～26 hours after pelletize, carries out plastic removal and obtain ceramic body after molding at 750～800 DEG C.
It is preferred that in step (c), during sintering, the ceramic powder identical with previously prepared constituent covers ceramic blank Body, sintering condition is to rise to 980～1020 DEG C with the programming rate of 2～5 DEG C/min, is incubated 2～5 hours, furnace cooling.
The present invention also provides for room temperature many ferrum ceramic component of a kind of high polarization intensity, its any of the above-described kind of room temperature many ferrum pottery Material is made.
It is preferred that after described room temperature many ferrum ceramic component is by becoming required size by described room temperature many ferrum Machining of Ceramics Prepared by silver, silver ink firing.
Accompanying drawing explanation
Fig. 1 and Fig. 2 is respectively the ceramic component of embodiment 2 and embodiment 3 gained ferroelectric hysteresis loop at room temperature and polarization Reverse current；
Fig. 3 is its dielectric constant of ceramic component and the dielectric loss variation with temperature of embodiment 2 gained；
Fig. 4 is the leakage current characteristic curve of embodiment 2 gained ceramic component；
Fig. 5 be embodiment 2 and embodiment 3 gained ceramic component room temperature under hysteresis curve.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment below in conjunction with accompanying drawing and following embodiment It is merely to illustrate the present invention, and the unrestricted present invention.
The present invention provides a kind of BiFeO with high polarization intensity3Basal cell Wen Duotie pottery, consisting of:
0.75((1-x)BiFeO3-xBiGaO3)-0.25Ba0.85Ca0.15Ti0.90Zr0.10O3+ 0.5wt%MnCO3。
The present invention introduces in BFO-BCZT system and is firstly introduced BiGaO3, devise a new BFO-BG-BCZT tri- Unit's system (ternary many ferrum ceramic material).Due to BiGaO3For super Tetragonal, c/a=1.30, its theoretical polarization intensity is up to 152 μC/cm2.Therefore, by introducing BiGaO3, both can be effectively improved the spontaneous polarization strength of system, simultaneously Ga ionic replacement Fe from Son can effective the appraising at the current rate of Fe in inhibition system, and then the resistivity of raising BFO system, finally realize the optimization of ferroelectric properties.
Wherein, 0 ＜ x≤0.05.If x is more than 0.05, system then has obvious dephasign (Bi2Fe4O9) generate.More Preferably, 0 ＜ x≤0.04.When 0 ＜ x≤0.04, generate without obvious dephasign, and material remanent polarization reaches as high as 43.86μC/cm2, and after polarization process, piezoelectric modulus is up to 90pC/N, and its remanent magnetization reaches as high as 0.27emu/ g。
Wherein MnCO3As additive, reduce system loss, wherein MnCO3Finally in system presented in manganese oxide In lattice, and addition should not too much be generally less than equal to 0.5wt%.
Under many ferrum pottery room temperature of the present invention, there is multiferroic, and insulating properties are good.After ferroelectric hysteresis loop is measured, wherein x When=0.02, the remanent polarization of pottery reaches as high as 43.86 μ C/cm2, this pottery has good ferromagnetic property simultaneously, Its saturation magnetization is up to 0.5660emu/g (20kOe), and remanent magnetization is about 0.2emu/g.
Many ferrum pottery room temperature of the present invention can be prepared by conventional solid-state method.Hereinafter, as example, its preparation side is described Method.
First, synthesizing ceramic powder.In one example, with Bi2O3、BaCO3、TiO2、ZrO2、CaCO3、MnCO3、 Fe2O3、Ga2O3Powder body is raw material, prepares according to the stoichiometric proportion of corresponding element.Should be understood that each raw material is not limited to above-mentioned, also It can be the material that can be decomposed into each metal-oxide through high temperature.Each raw material wet ball-milling method is mixed.Wet ball-milling method is mixed In material, can be according to raw material: ball: ethanol=1:(1.8～2.2): the mass ratio of (0.8～1.2), batch mixing 23～25 hours.Wherein Ball-milling medium can be zirconium ball or agate ball.Briquetting after drying, obtains ceramic powder after calcining.
Calcination condition can be: is warming up to 750～800 DEG C with the heating rate less than 5 DEG C/min, is incubated 2～5 hours, so Rear furnace cooling is to room temperature.
By the wet ball-milling method fine grinding of the ceramic powder of gained.In wet ball-milling method, according to ceramic powder: ball: ethanol= 1:(1.8～2.2): when the quality of (0.6～1.0) is less than fine grinding 23～25, so that the particle diameter of ceramic powder is less and distribution Narrow.Wherein ball-milling medium can be zirconium ball or agate ball.Ball milling post-drying.It is subsequently adding binding agent pelletize.The binding agent used It can be such as polyvinyl alcohol (PVA) etc..The addition of binding agent can be the 5～8wt.% of ceramic powder weight.After pelletize permissible It is aged 22～26 hours.
Ceramic particle is compressing, and then heat up plastic removal, obtains ceramic body.Plastic removal condition can be with less than 5 DEG C/ The heating rate of min is warming up to 980～1050 DEG C, is incubated 2～5 hours, and then furnace cooling is to room temperature.
The ceramic body of gained is put in alumina crucible, identical with the constituent of above-mentioned ceramic powder with having Ceramic powder covers ceramic body, is subsequently placed in high temperature furnace and obtains described ceramic material according to after certain sintering process sintering Material.
Sintering condition can be to be warming up to 980～1020 DEG C with the heating rate less than 5 DEG C/min, is incubated 2～5 hours, so Rear furnace cooling is to room temperature.
The present invention prepares the multiferroic ceramic material of a kind of excellent combination property by traditional solid reaction process, its tool There are high remanent polarization, excellent ferromagnetic property.Specifically, regulated and controled by component and process optimization, utilize tradition solid Phase method is prepared for having high remanent polarization (about 44 μ C/cm2), high ferromagnetic property (Mr=0.2emu/g, Hc= A kind of Novel Room Temperature many ferrum ceramic material 1.4kOe).This is significant for exploitation high-performance magnetism electric material.And this Invention uses conventional solid-state method to prepare, with low cost, it is easy to industrialized production.
The present invention also provides for the ferroelectric ceramics element being made up of above-mentioned many ferrum ceramic material.In one example, will sintering Good Machining of Ceramics becomes required size, the screen printing of silver paste, dries, obtains described ferroelectric ceramics element after silver ink firing.
Described silver ink firing condition can be to be warming up to 700～800 DEG C with the heating rate less than 2 DEG C/min and be incubated 20～40 Minute.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this Invention is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to this Some nonessential improvement and adjustment that bright foregoing is made belong to protection scope of the present invention.Following example is concrete Technological parameters etc. are the most only that an example in OK range, i.e. those skilled in the art can be done properly by explanation herein In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Method of testing:
The precise impedance analyser (LCR-HP4284A) using Agilent company of the U.S. connects Xi'an Communications University's electronic material The GJW-1 high-temperature dielectric temperature spectrum testing system of Research Institute or GermanyVT 7004 temperature-controlled cabinet of company is surveyed Electric capacity ceramic under examination different temperatures and frequency and loss.Utilize TF Analyzer 2000 ferroelectricity of aixACCT company of Germany Ferroelectric hysteresis loop and the Switching Currents loop line of pottery measured by analyser.Utilize the PPMS-9 of Quantum Design company of the U.S. Measure the magnetic performance of many ferrum pottery.
Embodiment 1:
The composition of many ferrum pottery:
0.75BiFeO3-0.25Ba0.85Ca0.15Ti0.90Zr0.10O3+ 0.5wt%MnCO3
(1) each constituent Bi in powder material is calculated by above-mentioned chemical formula composition2O3、BaCO3、TiO2、ZrO2、CaCO3、MnCO3、 Fe2O3Quality and press proportion of composing preparation, with wet ball-milling method mix, briquetting after drying, obtain ceramic powder after calcining, press According to raw material: ball: the mass ratio of ethanol=1:2:1 mixes 24 hours, makes each component mix homogeneously.After drying, cross 40 mesh sieves, pressure Block, is warming up to 800 DEG C with the heating rate less than 5 DEG C/min in air atmosphere, is incubated 5 hours synthesizing ceramic powders.
(2) ceramic powder of step (1) gained is ground and crosses 40 mesh sieves.According still further to raw material: ball: ethanol=1:2:0.8 Quality less than fine grinding 24 time, dry the ceramic powder after fine grinding.It is subsequently adding the PVA bonding that weight is powder weight 6wt.% Agent, pelletize, it is aged 24 hours, crosses 40 mesh sieves, compressing, then it is warmed up to 750 DEG C of plastic removals, obtains biscuit of ceramics.
(3) in order to prevent the volatilization of the elements such as bismuth, biscuit of ceramics is put into alumina crucible, with having and step (1) phase Being covered by base substrate with the ceramic powder of composition, cover ground lid, rise to 1020 DEG C with the heating rate of 5 DEG C/min, insulation 3 is little Time, obtain ceramic material sample after furnace cooling.
(4) the ceramic material sample wear down that will sinter, cleans, and dries, and silk screen printing silver is starched, then dries, with 2 DEG C/min Heating rate rise to 750 DEG C, obtain ceramic component after being incubated 30 minutes.
(5) the present embodiment pottery being carried out polarization process, polarization process can be: polarized electric field 4～8kV/mm, and temperature field is 50～120 DEG C, silicone oil keeps voltage 20～40 minutes.
(6) ceramic component to the present embodiment has carried out ferroelectric hysteresis loop, hysteresis curve and piezoelectric property under room temperature and has surveyed Examination, test result is shown in Table 1.
Embodiment 2:
The composition of many ferrum pottery:
0.75(0.98BiFeO3-0.02BiGaO3)-0.25Ba0.85Ca0.15Ti0.90Zr0.10O3+ 0.5wt%MnCO3
The preparation method of embodiment 1 is repeated by above-mentioned formula.
(1) ceramic component to the present embodiment carries out ferroelectric hysteresis loop, hysteresis curve and piezoelectric property under room temperature and measures, Test result is shown in Table 1.
(2) ceramic component to the present embodiment carries out the measurement of ferroelectric hysteresis loop under room temperature, and test result is shown in Fig. 1, remains pole Change intensity and reach 43.86 μ C/cm2, it can be observed that significantly current of polarization reversion peak, illustrate that electric field loads lower system inside and exists A large amount of electricdomain upsets, d after polarization process33For 90pC/N, illustrate that ceramic component ferroelectricity is excellent；Fig. 2 is to the present embodiment pottery Element carries out dielectric constant and the measurement of dielectric loss under different temperatures, finds that pottery has high Curie temperature (490～558 DEG C), and loss ceramic under high temperature is still for maintain than relatively low level (tan δ < 4%).Fig. 3 is the present embodiment ceramic component Leakage current characteristic characterize, it can be seen that BiFeO3Leakage current characteristic be improved significantly significantly reduce (J < 10-6A/cm2@4kV/ And leakage conductance mechanism is ohm conductance mechanisms mm),.Fig. 4 be the present embodiment ceramic component room temperature hysteresis measurement as a result, it is possible to Finding out that pottery hysteresis curve is obvious, remanent magnetization is about 0.2emu/g, and magnetic coercive field is 1.4kOe, and saturation magnetization is 0.5660emu/g (@20kOe), has good ferromagnetism.
Embodiment 3:
The composition of many ferrum pottery:
0.75(0.75BiFeO3-0.04BiGaO3)-0.25Ba0.85Ca0.15Ti0.90Zr0.10O3+ 0.5wt%MnCO3
The preparation method of embodiment 1 is repeated by above-mentioned formula.
(1) ceramic component to the present embodiment carries out ferroelectric hysteresis loop, hysteresis curve and piezoelectric property under room temperature and measures, Test result is shown in Table 1.
Listing the main results of embodiment 1,2,3 in table 1 below respectively, in table, Pr is remanent polarization, and Ms is Saturation magnetization, Mr is remanent magnetization, and Ec is magnetic coercive field；
The performance such as test condition (100mHz) under table 1 ceramic material room temperature and remanent polarization Pr
As it can be seen from table 1 by introducing BiGaO in BFO-BCZT system3, the multiferroic of system can be substantially improved Energy.

Claims (10)

1. room temperature many ferrum ceramic material, it is characterised in that the chemical composition of described room temperature many ferrum ceramic material is:
0.75((1-x)BiFeO3-xBiGaO3)-0.25Ba0.85Ca0.15Ti0.90Zr0.10O3+yMnCO3, wherein, 0 ＜x≤ 0.05, y≤0.5wt%。
Room temperature many ferrum ceramic material the most according to claim 1, it is characterised in that 0 ＜x≤0.04。
Room temperature many ferrum ceramic material the most according to claim 1 and 2, it is characterised in that described room temperature many ferrum ceramic material Remanent polarization can reach 22～44 μ C/cm2, after polarization processes, piezoelectric modulus can enough reach 90pC/N, residue The intensity of magnetization is 0.09～0.27emu/g.
4. the preparation method of the room temperature many ferrum ceramic material according to any one of a claims 1 to 3, it is characterised in that bag Include following steps:
A () solid phase method prepares ceramic powder, with Bi2O3、BaCO3、TiO2、ZrO2、CaCO3、MnCO3、Fe2O3、Ga2O3Powder body is former Material, prepares according to the stoichiometric proportion of corresponding element, and ball milling mixes, and briquetting obtains ceramic powder after calcining；
B (), by the ceramic powder ball milling of step (a) gained, pelletize, molding, obtains ceramic body；
C () obtains described many ferrum ceramic material after being sintered by the ceramic body of step (b) gained.
Preparation method the most according to claim 4, it is characterised in that in step (a), described ball milling is mixed into wet ball-milling Method mixes, according to raw material: abrading-ball: ethanol=1:(1.8～2.2): the mass ratio mixing of (0.7～1.0) 23～25 hours, wherein Abrading-ball is steel ball, zirconium ball or agate ball；Described calcining is to rise to 750～800 DEG C with the programming rate of 2～5 DEG C/min, is incubated 2 ～5 hours.
6., according to the preparation method described in claim 4 or 5, it is characterised in that in step (b), described ball milling uses wet type ball Mill method, according to ceramic powder: abrading-ball: ethanol=1:(1.8～2.2): the quality of (0.5～0.7) is than fine grinding, and wherein abrading-ball is steel Ball, zirconium ball or agate ball；The described wet ball-milling method fine grinding time is 23～25 hours, obtains ceramic powder after fine grinding.
7., according to the preparation method according to any one of claim 4 to 6, it is characterised in that in step (b), add binding agent Pelletize, the addition of binding agent is the 5～8wt.% of ceramic powder weight, is aged 22～26 hours, in 750 after molding after pelletize ～carry out plastic removal at 800 DEG C and obtain ceramic body.
8. according to the preparation method according to any one of claim 4 to 7, it is characterised in that in step (c), during sintering, with pre- The identical ceramic powder of the constituent first prepared covers ceramic body, and sintering condition is with the programming rate of 2～5 DEG C/min Rise to 980～1020 DEG C, be incubated 2～5 hours, furnace cooling.
9. room temperature many ferrum ceramic component of a high polarization intensity, it is characterised in that according to any one of claims 1 to 3 Room temperature many ferrum ceramic material make.
Room temperature many ferrum ceramic component of high polarization intensity the most according to claim 9, it is characterised in that described room temperature is many Ferrum ceramic component is by being prepared by silver, silver ink firing after described room temperature many ferrum Machining of Ceramics is become required size.
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