CN102875146B - Layered perovskite structural ceramic and preparation method thereof - Google Patents
Layered perovskite structural ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention provides layered perovskite structural ceramic and a preparation method thereof. The preparation method includes mixing well titanate compounds, bismuth compounds, lanthanum compounds, iron compounds, cobalt compounds and complexing agent in solvent, heating, evaporating and burning to obtain powder, and pre-sintering, preforming and sintering to obtain the layered perovskite structural ceramic structurally shown in a formula (I). Compared with ceramics prepared in prior art by solid phase sintering process, and the layered perovskite structural ceramic is prepared by solution process and sintering process. The preparation method has the advantages that the raw materials are spread evenly by the solution process, and the single-phase perovskite structural material is easy to obtain; the power prepared by the solution process has high reactivity, sintering temperature is low, the processes of ball-milling, binder removal and the like are avoided, and preparation cycle is shortened; by introducing lanthanum ions ferroelectric properties of the layered perovskite structural ceramic are improved, cobalt ions and ferric ions are coupled so that ferromagnetic properties of the ceramic are improved. The formula (I) is Bi7-xLaxFe1.5Co1.5Ti3O21.
Description
Technical field
The invention belongs to technical field of ceramic material, relate in particular to a kind of laminated perovskite structure pottery and preparation method thereof.
Background technology
Magnetoelectricity multi-ferroic material refers in certain warm area, shows ferroelectric order and Ferromagnetic/Antiferromagnetic order simultaneously, and has each other the material of certain coupling.In recent years, because multi-ferroic material not only can be used in the research and development of ferroelectric and magnetic apparatus, it can utilize the coupling between magnetoelectricity what is more important, applying electric field can regulate and control ferromagnetic polarization and apply magnetic field to regulate and control iron electric polarization, for design and the application of equipment provide additional one degree of freedom, thereby show very tempting prospect on emerging spintronics, polymorphic information storage, electric drive ferro-resonance device and magnetic tuning piezoelectric transducer.
In the multi-ferroic material of having found, bismuth be laminated perovskite structure material owing to containing Bi-O layer as space charge storehouse and insulation layer, can effectively reduce the leakage current in material, obtain people's extensive attention.There is simple uhligite ABO
3the BiFeO of type structure
3(BFO) be a kind of unleaded environmental friendliness shaped material, there is ferroelectrie Curie temperature and antiferromagnetic Neel temperature far above room temperature, but the preparation difficulty of its pure phase material, and higher oxygen vacancy concentration and Fe at a low price in material
2+the existence of ion easily causes high leakage conductance, destroys its ferroelectric properties, has limited the application of BFO material.Bismuth titanates (Bi
4ti
3o
12, BTO) and be also typical bismuth-containing laminated perovskite structure, it has higher Curie temperature and spontaneous polarization, and its stronger ferroelectricity is from Bi
3+the 6s of ion
2lone electron pair.
BFO material combines with BTO material, and can to form structural formula be Bi
n+1fe
n-3ti
3o
3 (n+1)the laminated perovskite multi-ferroic material of (wherein n is equal to or greater than 3 integer, BFTO), 2 bismuth oxygen layer (Bi
2o
2)
2+between contain octahedra and one or more (Fe-O) octahedron of 3 titanyls (Ti-O), its multiferroic derives from respectively ferroelectric cell (BTO) and many iron unit (BFO).BFTO can effectively utilize the insulating effect of bismuth oxygen layer to suppress the leakage current that magnet unit causes due to oxygen room and Fe multivalence state, but it still shows as room temperature antiferromagnetism, is restricted in actual applications.Result of study shows that the doping of A position can improve the ferroelectric properties of material, reduces the leakage current of sample; The doping of B position can improve the ferromagnetic property of material.
Publication number is that the Chinese patent of CN102167584A discloses a kind of five laminate structure ferrotianium cobalt acid bismuth stupaliths with multi-ferrum property and preparation method thereof, at B position doping cobalt ion, can realize the coupling between iron cobalt ion, and then the ferromagnetic property of raising material, but the ferroelectric properties of material does not improve, and employing solid-phase sintering process, sintering temperature is higher.Publication number is that the Chinese patent of CN 101704669A discloses a kind of laminate structure ferrotitanium lanthanum bismuth cobaltate ceramic with multi-ferrum property and preparation method thereof, the lanthanum ion of its high valence state that adulterates in A position, B position doping Co ion, improve ferroelectric properties and the ferromagnetic property of material simultaneously, but its preparation method is similarly solid reaction process, need through ball milling, pre-synthesis, moulding, plastic removal and sintering process, preparation cycle is long, and is difficult to obtain pure phase powder.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of laminated perovskite structure pottery and preparation method thereof, and this pottery is to have good ferroelectric properties and ferromagnetic property, and preparation cycle is short.
The invention provides a kind of laminated perovskite structure pottery, as shown in the formula (I):
Bi
7-xLa
xFe
1.5Co
1.5Ti
3O
21 （I）
Wherein, 0.2≤x≤1.5.
The preparation method who the invention provides a kind of laminated perovskite structure pottery, comprises the following steps:
A) bismuth source compound, lanthanum source compound, Fe source compound, cobalt source compound and titanate ester compound are dissolved in to solvent in the ratio of metal ion Bi:La:Fe:Co:Ti=7-x:x:1.5:1.5:3, add complexing agent mix and blend, regulate behind pH value to 5 ~ 7, heating evaporate to dryness burns into powder, after pre-burning, obtain powder, wherein 0.2≤x≤1.5;
B), by described powder compressing tablet, sintering, obtains laminated perovskite structure pottery.
Preferably, described bismuth source compound is selected from the one in Bismuth trinitrate, bismuth subnitrate, bismuth oxide, Bismuth Subcarbonate and Oxalic acid bismuth salt.
Preferably, described lanthanum source compound is selected from the one in lanthanum nitrate, Phosbloc, lanthanum trioxide, lanthanum oxalate and lanthanum acetate.
Preferably, described Fe source compound is selected from the one in iron nitrate, ferric oxide, Z 250 and ironic oxalate.
Preferably, described cobalt source compound is selected from the one in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt oxide, cobalt oxalate and cobaltous acetate.
Preferably, described complexing agent is selected from one or more in ethylenediamine tetraacetic acid (EDTA), citric acid and glycine.
Preferably, the mol ratio of described complexing agent and metal ion sum is 1 ~ 2.5:1.
Preferably, the temperature of described pre-burning is 700 DEG C ~ 800 DEG C, and the time is 2 ~ 4h.
Preferably, be sintered to hot pressed sintering or retort furnace sintering.
The invention provides a kind of laminated perovskite structure pottery and preparation method thereof, the method is by titanate ester compound, bismuth source compound, lanthanum source compound, Fe source compound, cobalt source compound and complexing agent mix and blend in solvent according to a certain percentage, regulate behind pH value to 5 ~ 7, heating evaporate to dryness burns into powder, obtains powder after pre-burning; By described powder compressing tablet, after sintering, obtain the laminated perovskite structure pottery of formula (I) structure.Compared with preparing ferrotitanium lanthanum bismuth cobaltate ceramic with available technology adopting solid-phase sintering process, the present invention adopts solution method and sintering process to prepare laminated perovskite structure pottery.First, adopt solution method preparation, raw material is uniformly dispersed, gained powder granule is thin, component is even, is easy to obtain the material of single-phase laminated perovskite structure; Secondly, powder prepared by solution method has higher reactive behavior, thereby makes the temperature of sintering relatively low, and without through processes such as ball milling and plastic removals, has shortened preparation cycle; Again, the introducing of lanthanum ion has improved on the one hand because of the bismuth ion leakage current that causes oxygen room to increase that volatilizees, because can causing lattice, the difference of lanthanum and bismuth ion radius produces distortion on the other hand, improve ceramic ferroelectric properties, cobalt ion and iron ion coupling, improved ceramic ferromagnetic property simultaneously.
Experimental result shows, the laminated perovskite structure pottery that the present invention prepares is the single-phase laminated perovskite structure pottery of six laminate structures, measuring under the condition that electric field is 100kV/cm, and remnant polarization is 1.35 ~ 2.61 μ C/cm
2, coercive field is 23 ~ 40kV/cm, is measuring under the condition that electric field is 150kV/cm, remnant polarization is 4.99 ~ 7.48 μ C/cm
2, coercive field (2E
c) be 67 ~ 88kV/cm, under normal temperature condition, remanence rate is 1.12 ~ 2.60emu/g, coercive field (2H
c) be 250 ~ 360 Oe.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the laminated perovskite structure pottery that makes in the embodiment of the present invention 1;
Fig. 2 is the stereoscan photograph of the laminated perovskite structure pottery that makes in the embodiment of the present invention 1;
Fig. 3 is the ferroelectric properties survey sheet of the laminated perovskite structure pottery that makes in the embodiment of the present invention 1;
Fig. 4 is the ferromagnetic property survey sheet of the laminated perovskite structure pottery that makes in the embodiment of the present invention 1.
Embodiment
The invention provides a kind of laminated perovskite structure pottery, as shown in the formula (I):
Bi
7-xLa
xFe
1.5Co
1.5Ti
3O
21（I）
Wherein, 0.2≤x≤1.5, are preferably 0.4≤x≤1.3, more preferably 0.6≤x≤1.2.
The structure of the laminated perovskite structure pottery of formula of the present invention (I) structure is 2 bismuth oxygen layer ((Bi
2o
2)
2+) between accompany that 3 titanyls (Ti-O) are octahedra, 1.5 iron oxygen (Fe-O) octahedra and 1.5 cobalt oxygen (Co-O) octahedron.
In perovskite structure pottery, due to the multivalence state of magnetic ion iron ion and the bismuth element oxygen room of causing of volatilizing, therefore easily cause the increase of leakage current.Laminated perovskite structure pottery bismuth-containing oxygen layer of the present invention, can play the effect of space charge storehouse and insulation layer, can reduce the leakage current causing due to the multivalence state of magnetic ion Fe; Can reduce because of the bismuth ion leakage current increasing that volatilizees at the not volatile rare earth element lanthanum ion of A position doping, the ferroelectric properties of laminated perovskite structure pottery is provided; At B position doping cobalt ion, iron and cobalt are the magnetic particle having less than d electron structure, and both can be coupled, and have improved the ferromagnetic property of stupalith, therefore, laminated perovskite structure pottery provided by the invention has good ferroelectric properties and ferromagnetic property.
The present invention also provides above-mentioned laminated perovskite structure pottery corresponding preparation method, comprise the following steps: A) titanate ester compound, bismuth source compound, lanthanum source compound, Fe source compound and cobalt source compound are dissolved in to solvent in proportion, add complexing agent mix and blend, after pH value is adjusted to 5 ~ 7, heating evaporate to dryness burns into powder, obtains powder after pre-burning; B), by described powder compressing tablet, sintering, obtains laminated perovskite structure pottery.
In order to clearly demonstrate the present invention, below respectively the experimentation of steps A and step B is described in detail.
Described steps A is specially: by bismuth source compound, lanthanum source compound, Fe source compound, cobalt source compound and titanate ester compound are dissolved in solvent in the ratio of metal ion Bi:La:Fe:Co:Ti=7-x:x:1.5:1.5:3, add complexing agent mix and blend, after pH value is adjusted to 5 ~ 7, be preferably 6 ~ 7, obtain settled solution, heating evaporate to dryness burns into powder, put in retort furnace 700 DEG C ~ 800 DEG C, be preferably after 720 DEG C ~ 780 DEG C pre-burning 2 ~ 4h, be preferably 3 ~ 4h, obtain powder, wherein 0.2≤x≤1.5, be preferably 0.4≤x≤1.3, more preferably 0.6≤x≤1.2.Wherein, the order of addition(of ingredients) of described bismuth source compound, lanthanum source compound, Fe source compound, cobalt source compound, titanate ester compound and complexing agent there is no special restriction.
Wherein, described titanate ester compound is titanate ester compound well known to those skilled in the art, is preferably tetrabutyl titanate.Described bismuth source compound, lanthanum source compound, Fe source compound and cobalt source compound are selected according to the principle of not introducing other impurity, the compound of selecting impurity easily to remove by burning.
The source compound of bismuth described in the present invention is selected from the one in Bismuth trinitrate, bismuth subnitrate, bismuth oxide, Bismuth Subcarbonate and Oxalic acid bismuth salt, is preferably Bismuth trinitrate; Described lanthanum source compound is selected from the one in lanthanum nitrate, Phosbloc, lanthanum trioxide, lanthanum oxalate and lanthanum acetate, is preferably lanthanum nitrate; Described Fe source compound is selected from the one in iron nitrate, ferric oxide, Z 250 and ironic oxalate, is preferably iron nitrate; Described cobalt source compound is selected from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt oxide, cobalt oxalate and cobaltous acetate, is preferably Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
Thereby solvent described in steps A can be selected corresponding solvent according to bismuth source compound, lanthanum source compound, Fe source compound and cobalt source compound, is preferably nitric acid, oxalic acid or acetic acid, more preferably nitric acid.
Described complexing agent is selected from one or more in ethylenediamine tetraacetic acid (EDTA), citric acid and glycine, in described complexing agent and solution, the mol ratio of all metal ions is 1 ~ 2.5:1, be preferably 1.4 ~ 2:1, more preferably 1.5 ~ 1.9:1, described complexing agent is preferably ethylenediamine tetraacetic acid (EDTA) and citric acid, in itself and solution, the mol ratio of all metal ions is 0.5 ~ 1.5:1:1, is preferably 0.7 ~ 1.2:1:1.
Described pH value conditioning agent is preferably quadrol or ammoniacal liquor, can remove corresponding element by burning, and not introduce other impurity.
In the present invention, by burning into powder, can tentatively remove organic phase wherein; Burn in step can further be removed remaining carbon and nitrogen element, is also the step of material preformation phase simultaneously.
According to the present invention, the selected compound of raw material titanate ester compound, bismuth source compound, lanthanum source compound, Fe source compound and cobalt source compound is all required to be chemical pure, and the purity of compound used therefor is higher, and the performance of gained laminated perovskite structure pottery is better.
In described steps A, the preparation of powder adopts the improvement Pechini method of carrying out in solution, compared with solid reaction process, the inventive method is fully uniformly dispersed raw material titanate ester compound, bismuth source compound, lanthanum source compound, Fe source compound and cobalt source compound, the particle of gained powder more carefully, more even, be easy to obtain single-phase laminated perovskite structure pottery; And the inventive method also has the advantage in reactive behavior, Fe-Co ion is fully coupled, thereby obtains higher ferromagnetic property, meanwhile, lanthanum ion also easily enters the A position of perovskite structure, reduces leakage current, and ferroelectric properties is improved; Adopt solution method to be prepared powder, without through steps such as ball milling, pre-synthesis, plastic removals, after compressing tablet, directly carry out sintering, shortened preparation cycle, and the activity of gained powder is higher, thereby has reduced the temperature of sintering, reduced the volatilization of bismuth ion.
Described step B is specially: the condition lower sheeting that is 60 ~ 150MPa at pressure by described powder, be preferably 80 ~ 100MPa, and obtain the cylindrical samples that thickness is 3 ~ 5mm, be preferably 4 ~ 5mm; Then described cylindrical samples is carried out to sintering.Described hot pressed sintering or the retort furnace sintering of being sintered to, is preferably hot pressed sintering, adopts hot pressed sintering can at relatively low temperature, obtain the high-performance ceramic that sintering degree is higher and density is higher, reduces the volatilization of bismuth element.
The step of described retort furnace sintering is step well known to those skilled in the art, there is no special restriction, and its sintering temperature is 600 DEG C ~ 1000 DEG C, is preferably 800 DEG C ~ 950 DEG C, and sintering time is 2 ~ 6h, is preferably 3 ~ 5h.
The concrete steps of described hot pressed sintering are: described cylindrical samples is placed in by ZrO
2in the corundum mould or silicon carbide mould of powder or MgO powder inner lining protection; under the environment of protective atmosphere, be warming up to 600 DEG C ~ 800 DEG C; be preferably 650 DEG C ~ 750 DEG C; be forced into 5 ~ 20MPa; be preferably 10 ~ 20MPa; extremely release completely after 800 DEG C ~ 1000 DEG C insulation 1 ~ 6h of the highest sintering temperature, is preferably 3 ~ 5h, obtains laminated perovskite structure pottery.Described protective atmosphere is protective atmosphere well known to those skilled in the art, is preferably one or more in argon gas, oxygen and nitrogen.
According to the present invention, the structure optimization of described cylindrical samples is the powder of gained powder external parcel bismuth element excessive 10 ~ 20% in above-mentioned steps A.The effect of a volatile element atmosphere sintering can be provided as protective layer using the surrounding layer of same element, block in sample element to non-same element surrounding layer ZrO
2the passage of powder or the diffusion of MgO powder, can protect internal layer sample component, is mainly the accuracy of the cobalt element content of volatile bismuth element and easy diffusion, meanwhile, also has the effect of thermal stresses buffering with the surrounding layer of element.The preparation method of the powder of described bismuth element excessive 10 ~ 20% is identical with the preparation method of gained powder in internal layer steps A, and difference is only the content of bismuth element.
Non-same element surrounding layer ZrO
2the effect of powder or MgO powder is to utilize its high-melting-point and high sintering temperature, reaches the object of isolation sample and mould, is convenient to the demoulding after hot pressed sintering; The effect that it also has thermal stresses buffering reaches the object of protecting sample and mould simultaneously.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of laminated perovskite structure pottery provided by the invention and preparation method thereof is described in detail.
In following examples, agents useful for same is commercially available, raw materials used tetrabutyl titanate, five nitric hydrate bismuths, nitric hydrate lanthanum, Fe(NO3)39H2O, Cobaltous nitrate hexahydrate, ethylenediamine tetraacetic acid (EDTA) and monohydrate potassium are traditional Chinese medicines group analytical reagent, and its specification is as shown in table 1.
The specification that table 1 is raw materials used
Embodiment 1
1.1 are dissolved in 21.0269g five nitric hydrate bismuths, 2.6444g nitric hydrate lanthanum, 4.3948g Fe(NO3)39H2O, 3.1504g Cobaltous nitrate hexahydrate, 7.4424g tetrabutyl titanate, 19.6124g citric acid and 18.9965g ethylenediamine tetraacetic acid (EDTA) in nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed on heating in crucible and concentrate until solution evaporate to dryness burns into powder, in retort furnace, 750 DEG C of pre-burning 3h, obtain powder.
Under 1.2 conditions that are 80MPa by the powder obtaining in 1.1 at pressure, cylindrical samples is made in dry-pressing, sample size diameter 15mm, thickness 4mm, cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder obtaining in 1.1, the surrounding layer of bismuth element excessive 10% is identical with 1.1 preparation method, and difference is the content excessive 10% of five nitric hydrate bismuths.
1.3 by the cylindrical samples obtaining in 1.2, and being placed in liner is ZrO
2in the corundum mould of powder protection, under the atmosphere that is 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 DEG C, start pressurization, after 830 DEG C, 10MPa heat-insulation pressure keeping 3h, be cooled to room temperature, obtain the ceramic Bi of laminated perovskite structure
6laFe
1.5co
1.5ti
3o
21.
Utilize X-ray diffractometer (the Rigaku TTR III of Rigaku motor company type) to the laminated perovskite structure pottery Bi obtaining in 1.3
6laFe
1.5co
1.5ti
3o
21carry out structural analysis, obtain its X-ray diffractogram, as shown in Figure 1, result shows, sample is the ceramics sample of single Aurivillius structure, there is no obvious second-phase.
Utilize scanning electronic microscope (the JEOL JSM-6390LA of Jeol Ltd. type) to the laminated perovskite structure pottery Bi obtaining in 1.3
6laFe
1.5co
1.5ti
3o
21carry out morphology observation, obtain its stereoscan photograph, as shown in Figure 2, result shows, its sintering degree is better, and grain shape size is basically identical, and thing pore exists, and the density of pottery is better.
Utilize ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 1.3
6laFe
1.5co
1.5ti
3o
21carry out ferroelectric properties test, obtain its ferroelectric properties survey sheet, as shown in Figure 3, result shows, pottery is measured under the condition that electric field is 150kV/cm at normal temperature, remnant polarization (2P
r) be 7.48 μ C/cm
2, coercive field (2E
c) be 88kV/cm.
Utilize vibrating sample magnetometer (EV7 of ADE Co. of U.S. type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 1.3
6laFe
1.5co
1.5ti
3o
21carry out ferromagnetic property test, obtain its ferromagnetic property survey sheet, as shown in Figure 4, result shows, the remanence rate (2M of pottery
r) be 1.12emu/g, coercive field (2H
c) be 360Oe.
Embodiment 2
2.1 are dissolved in 21.0269g five nitric hydrate bismuths, 2.6444g nitric hydrate lanthanum, 4.3948g Fe(NO3)39H2O, 3.1504g Cobaltous nitrate hexahydrate, 7.4424g tetrabutyl titanate, 19.6124g citric acid and 18.9965g ethylenediamine tetraacetic acid (EDTA) in nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed on heating in crucible and concentrate until solution evaporate to dryness burns into powder, in retort furnace, 750 DEG C of pre-burning 3h, obtain powder.
Under 2.2 conditions that are 80MPa by the powder obtaining in 2.1 at pressure, cylindrical samples is made in dry-pressing, sample size diameter 15mm, thickness 2mm, cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder obtaining in 2.1, the surrounding layer of bismuth element excessive 10% is identical with 2.1 preparation method, and difference is the content excessive 10% of five nitric hydrate bismuths.
2.3 by the cylindrical samples obtaining in 2.2, is placed in retort furnace, is warming up to 950 DEG C in air atmosphere, after sintering 5h, obtains laminated perovskite structure pottery Bi
6laFe
1.5co
1.5ti
3o
21.
Utilize ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type) to the laminated perovskite structure pottery Bi obtaining in 2.3
6laFe
1.5co
1.5ti
3o
21carry out at normal temperatures ferroelectric properties test, obtain its ferroelectric properties, measure under the condition that electric field is 150kV/cm remnant polarization (2P at normal temperature
r) be 4.99 μ C/cm
2, coercive field (2E
c) be 67kV/cm.
Utilize vibrating sample magnetometer (EV7 of ADE Co. of U.S. type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 2.3
6laFe
1.5co
1.5ti
3o
21carry out ferromagnetic property test, obtain its ferromagnetic property, remanence rate (2M
r) be 1.93emu/g, coercive field (2H
c) be 344Oe.
Embodiment 3
3.1 are dissolved in 21.9033g five nitric hydrate bismuths, 1.9846g nitric hydrate lanthanum, 4.3947g Fe(NO3)39H2O, 3.1500g Cobaltous nitrate hexahydrate, 7.4423g tetrabutyl titanate, 19.6325g citric acid and 18.9988g ethylenediamine tetraacetic acid (EDTA) in nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed on heating in crucible and concentrate until solution evaporate to dryness burns into powder, in retort furnace, 750 DEG C of pre-burning 3h, obtain powder.
Under 3.2 conditions that are 80MPa by the powder obtaining in 3.1 at pressure, cylindrical samples is made in dry-pressing, sample size diameter 15mm, thickness 4mm, cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder obtaining in 3.1, the surrounding layer of bismuth element excessive 10% is identical with 3.1 preparation method, and difference is the content excessive 10% of five nitric hydrate bismuths.
3.3 by the cylindrical samples obtaining in 3.2, and being placed in liner is ZrO
2in the corundum mould of powder protection, under the atmosphere that is 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 DEG C, start pressurization, after 830 DEG C, 10MPa heat-insulation pressure keeping 3h, be cooled to room temperature, obtain the ceramic Bi of laminated perovskite structure
6.25la
0.75fe
1.5co
1.5ti
3o
21.
Utilize ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 3.3
6.25la
0.75fe
1.5co
1.5ti
3o
21carry out ferroelectric properties test, obtain its ferroelectric properties, measure under the condition that electric field is 100kV/cm remnant polarization (2P at normal temperature
r) be 2.61 μ C/cm
2, coercive field (2E
c) be 40kV/cm.
Utilize vibrating sample magnetometer (EV7 of ADE Co. of U.S. type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 3.3
6.25la
0.75fe
1.5co
1.5ti
3o
21carry out ferromagnetic property test, obtain its ferromagnetic property, remanence rate (2M
r) be 2.60emu/g, coercive field (2H
c) be 344Oe.
Embodiment 4
4.1 are dissolved in 22.7791g five nitric hydrate bismuths, 1.3225g nitric hydrate lanthanum, 4.3955g Fe(NO3)39H2O, 3.1501g Cobaltous nitrate hexahydrate, 7.4428g tetrabutyl titanate, 19.6091g citric acid and 1809986g ethylenediamine tetraacetic acid (EDTA) in nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed on heating in crucible and concentrate until solution evaporate to dryness burns into powder, in retort furnace, 750 DEG C of pre-burning 3h, obtain powder.
Under 4.2 conditions that are 80MPa by the powder obtaining in 4.1 at pressure, cylindrical samples is made in dry-pressing, sample size diameter 15mm, thickness 4mm, cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder obtaining in 4.1, the surrounding layer of bismuth element excessive 10% is identical with 4.1 preparation method, and difference is the content excessive 10% of five nitric hydrate bismuths.
4.3 by the cylindrical samples obtaining in 4.2, and being placed in liner is ZrO
2in the corundum mould of powder protection, under the atmosphere that is 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 DEG C, start pressurization, after 830 DEG C, 10MPa heat-insulation pressure keeping 3h, be cooled to room temperature, obtain the ceramic Bi of laminated perovskite structure
6.5la
0.5fe
1.5co
1.5ti
3o
21.
Utilize ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 4.3
6.5la
0.5fe
1.5co
1.5ti
3o
21carry out ferroelectric properties test, obtain its ferroelectric properties, measure under the condition that electric field is 100kV/cm remnant polarization (2P at normal temperature
r) be 1.53 μ C/cm
2, coercive field (2E
c) be 32kV/cm.
Utilize vibrating sample magnetometer (EV7 of ADE Co. of U.S. type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 4.3
6.5la
0.5fe
1.5co
1.5ti
3o
21carry out ferromagnetic property test, obtain its ferromagnetic property, remanence rate (2M
r) be 1.38emu/g, coercive field (2H
c) be 257Oe.
Embodiment 5
5.1 are dissolved in 23.6287g five nitric hydrate bismuths, 0.6617g nitric hydrate lanthanum, 4.3950g Fe(NO3)39H2O, 3.1507g Cobaltous nitrate hexahydrate, 7.4430g tetrabutyl titanate, 19.6824g citric acid and 19.0010g ethylenediamine tetraacetic acid (EDTA) in nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed on heating in crucible and concentrate until solution evaporate to dryness burns into powder, in retort furnace, 750 DEG C of pre-burning 3h, obtain powder.
Under 5.2 conditions that are 80MPa by the powder obtaining in 5.1 at pressure, cylindrical samples is made in dry-pressing, sample size diameter 15mm, thickness 4mm, cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder obtaining in 5.1, the surrounding layer of bismuth element excessive 10% is identical with 5.1 preparation method, and difference is the content excessive 10% of five nitric hydrate bismuths.
5.3 by the cylindrical samples obtaining in 5.2, and being placed in liner is ZrO
2in the corundum mould of powder protection, under the atmosphere that is 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 DEG C, start pressurization, after 830 DEG C, 10MPa heat-insulation pressure keeping 3h, be cooled to room temperature, obtain the ceramic Bi of laminated perovskite structure
6.75la
0.25fe
1.5co
1.5ti
3o
21.
Utilize ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 5.3
6.75la
0.25fe
1.5co
1.5ti
3o
21carry out ferroelectric properties test, obtain its ferroelectric properties, measure under the condition that electric field is 100kV/cm remnant polarization (2P at normal temperature
r) be 1.89 μ C/cm
2, coercive field (2E
c) be 40kV/cm.
Utilize vibrating sample magnetometer (EV7 of ADE Co. of U.S. type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 5.3
6.75la
0.25fe
1.5co
1.5ti
3o
21carry out ferromagnetic property test, obtain its ferromagnetic property, remanence rate (2M
r) be 1.20emu/g, coercive field (2H
c) be 250Oe.
Embodiment 6
6.1 are dissolved in 20.1253g five nitric hydrate bismuths, 3.3055g nitric hydrate lanthanum, 4.3947g Fe(NO3)39H2O, 3.1501g Cobaltous nitrate hexahydrate, 7.4424g tetrabutyl titanate, 19.6424g citric acid and 19.0040g ethylenediamine tetraacetic acid (EDTA) in nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed on heating in crucible and concentrate until solution evaporate to dryness burns into powder, in retort furnace, 750 DEG C of pre-burning 3h, obtain powder.
Under 6.2 conditions that are 80MPa by the powder obtaining in 6.1 at pressure, cylindrical samples is made in dry-pressing, sample size diameter 15mm, thickness 4mm, cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder obtaining in 6.1, the surrounding layer of bismuth element excessive 10% is identical with 6.1 preparation method, and difference is the content excessive 10% of five nitric hydrate bismuths.
6.3 by the cylindrical samples obtaining in 6.2, and being placed in liner is ZrO
2in the corundum mould of powder protection, under the atmosphere that is 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 DEG C, start pressurization, after 830 DEG C, 10MPa heat-insulation pressure keeping 3h, be cooled to room temperature, obtain the ceramic Bi of laminated perovskite structure
5.75la
1.25fe
1.5co
1.5ti
3o
21.
Utilize ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 6.3
5.75la
1.25fe
1.5co
1.5ti
3o
21carry out ferroelectric properties test, obtain its ferroelectric properties, measure under the condition that electric field is 100kV/cm remnant polarization (2P at normal temperature
r) be 1.35 μ C/cm
2, coercive field (2E
c) be 23kV/cm.
Utilize vibrating sample magnetometer (EV7 of ADE Co. of U.S. type) at normal temperatures to the laminated perovskite structure pottery Bi obtaining in 6.3
5.75la
1.25fe
1.5co
1.5ti
3o
21carry out ferromagnetic property test, obtain its ferromagnetic property, remanence rate (2M
r) be 1.64emu/g, coercive field (2H
c) be 290Oe.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a laminated perovskite structure pottery, shown in (I):
Bi
7-xLa
xFe
1.5Co
1.5Ti
3O
21 (I)
Wherein, x is 0.25,0.5,0.75,1 or 1.25.
2. a preparation method for laminated perovskite structure pottery, is characterized in that, comprises the following steps:
A) bismuth source compound, lanthanum source compound, Fe source compound, cobalt source compound and titanate ester compound are dissolved in to solvent in the ratio of metal ion Bi:La:Fe:Co:Ti=7-x:x:1.5:1.5:3, add complexing agent mix and blend, regulate behind pH value to 5～7, heating evaporate to dryness burns into powder, after pre-burning, obtain powder, wherein x is 0.25,0.5,0.75,1 or 1.25; Described complexing agent is selected from ethylenediamine tetraacetic acid (EDTA) and citric acid;
B), by described powder compressing tablet, sintering, obtains laminated perovskite structure pottery;
The described hot pressed sintering that is sintered to, comprising: it is ZrO that the sample after compressing tablet is placed in to liner
2in the corundum mould of powder protection, under the atmosphere that is 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 DEG C, start to pressurize, after 830 DEG C, 10MPa heat-insulation pressure keeping 3h, be cooled to room temperature.
3. preparation method according to claim 2, is characterized in that, described bismuth source compound is selected from the one in Bismuth trinitrate, bismuth subnitrate, bismuth oxide, Bismuth Subcarbonate and Oxalic acid bismuth salt.
4. preparation method according to claim 2, is characterized in that, described lanthanum source compound is selected from the one in lanthanum nitrate, Phosbloc, lanthanum trioxide, lanthanum oxalate and lanthanum acetate.
5. preparation method according to claim 2, is characterized in that, described Fe source compound is selected from the one in iron nitrate, ferric oxide, Z 250 and ironic oxalate.
6. preparation method according to claim 2, is characterized in that, described cobalt source compound is selected from the one in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt oxide, cobalt oxalate and cobaltous acetate.
7. preparation method according to claim 2, is characterized in that, the mol ratio of described complexing agent and metal ion sum is 1～2.5:1.
8. preparation method according to claim 2, is characterized in that, the temperature of described pre-burning is 700 DEG C～800 DEG C, and the time is 2～4h.
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| A. Srinivas et al..INVESTIGATION OF DIELECTRIC AND MAGNETIC NATURE OF Bi7Fe3Ti3O21.《Materials Research Bulletin》.1999,第34卷(第6期),第989-996页. |
| Ba1-xBixTi1-yMnyO3和Bi5-xLaxTi3Fe1-yCoyO15多铁陶瓷的磁性、铁电性以及介电性的研究;汪川惠;《中国博士学位论文全文数据库 工程科技I辑》;20110915(第9期);第56-57、71页 * |
| INVESTIGATION OF DIELECTRIC AND MAGNETIC NATURE OF Bi7Fe3Ti3O21;A. Srinivas et al.;《Materials Research Bulletin》;19991231;第34卷(第6期);第989-996页 * |
| 汪川惠.Ba1-xBixTi1-yMnyO3和Bi5-xLaxTi3Fe1-yCoyO15多铁陶瓷的磁性、铁电性以及介电性的研究.《中国博士学位论文全文数据库 工程科技I辑》.2011,(第9期),第56-57、71页. |
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