CN102875146A - 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
The magnetoelectricity multi-ferroic material refers in certain warm area, shows simultaneously ferroelectric order and Ferromagnetic/Antiferromagnetic order, 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 coupling between the magnetoelectricity what is more important, namely applying electric field can regulate and control ferromagnetic polarization and apply magnetic field to regulate and control iron electric polarization, for the design of equipment and application provide additional one degree of freedom, thereby in emerging spintronics, the storage of polymorphic information, electricity drives the ferro-resonance device and the magnetic tuning piezoelectric transducer shows very tempting prospect.
In the multi-ferroic material of having found, bismuth is the laminated perovskite structure material owing to containing the Bi-O layer as space charge storehouse and insulation layer, can effectively reduce the leakage current in the material, obtains people's extensive attention.Has simple uhligite ABO
3The BiFeO of type structure
3(BFO) be a kind of unleaded environmental friendliness shaped material, have ferroelectrie Curie temperature and antiferromagnetic Neel temperature far above room temperature, but its pure phase material preparation difficulty, and higher oxygen vacancy concentration and Fe at a low price in the 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, also be typical bismuth-containing laminated perovskite structure BTO), it has higher Curie temperature and spontaneous polarization, and its stronger ferroelectricity is from Bi
3+The 6s of ion
2Lone electron pair.
The BFO material combines with the BTO material, and can to form structural formula be Bi
N+1Fe
N-3Ti
3O
3 (n+1)(wherein n is equal to or greater than 3 integer, laminated perovskite multi-ferroic material 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 many iron property derives from respectively ferroelectric cell (BTO) and many iron unit (BFO).BFTO can effectively utilize the insulating effect of bismuth oxygen layer to suppress magnet unit because the leakage current that oxygen room and Fe multivalence attitude cause, but it still shows as the 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; Mix and can improve the ferromagnetic property of material in the B position.
Publication number is that the Chinese patent of CN102167584A discloses a kind of five laminate structure ferrotianium cobalts acid bismuth stupalith with multi-ferrum property and preparation method thereof, at B position doping cobalt ion, can realize the coupling between the iron cobalt ion, and then the ferromagnetic property of raising material, but the ferroelectric properties of material does not improve, and the 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 mixes in the A position, B position doping Co ion, improve simultaneously ferroelectric properties and the ferromagnetic property of material, 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 the 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 invention provides a kind of preparation method of laminated perovskite structure pottery, may further comprise the steps:
A) 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 the complexing agent mix and blend, after regulating pH value to 5 ~ 7, the heating evaporate to dryness burns into powder, obtain powder after the pre-burning, wherein 0.2≤x≤1.5;
B) with described powder compressing tablet, sintering obtains the laminated perovskite structure pottery.
Preferably, described bismuth source compound is selected from a kind of in Bismuth trinitrate, bismuth subnitrate, bismuth oxide, Bismuth Subcarbonate and the Oxalic acid bismuth salt.
Preferably, described lanthanum source compound is selected from a kind of in lanthanum nitrate, Phosbloc, lanthanum trioxide, lanthanum oxalate and the lanthanum acetate.
Preferably, described Fe source compound is selected from a kind of in iron nitrate, ferric oxide, Z 250 and the ironic oxalate.
Preferably, described cobalt source compound is selected from a kind of in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt oxide, cobalt oxalate and the cobaltous acetate.
Preferably, described complexing agent is selected from one or more in ethylenediamine tetraacetic acid (EDTA), citric acid and the 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 ℃ ~ 800 ℃, 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 with 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, after regulating pH value to 5 ~ 7, the heating evaporate to dryness burns into powder, obtains powder after the pre-burning; With described powder compressing tablet, behind the sintering, obtain the laminated perovskite structure pottery of formula (I) structure.Prepare ferrotitanium lanthanum bismuth cobaltate ceramic with the available technology adopting solid-phase sintering process and compare, the present invention adopts solution method and sintering process to prepare the laminated perovskite structure pottery.At first, adopt the solution method preparation, so that raw material is uniformly dispersed, the gained powder granule is thin, component is even, is easy to obtain the material of single-phase laminated perovskite structure; Secondly, the powder of solution method preparation has higher reactive behavior, thereby makes the temperature of sintering relatively low, and need not to have shortened preparation cycle through processes such as ball milling and plastic removals; Again, the introducing of lanthanum ion has improved the leakage current that causes the oxygen room to increase because of the bismuth ion volatilization on the one hand, on the other hand because the difference of lanthanum and bismuth ion radius can cause lattice to produce distortion, improved ceramic ferroelectric properties, simultaneously cobalt ion and iron ion coupling has improved ceramic ferromagnetic property.
Experimental result shows, the laminated perovskite structure pottery that the present invention prepares is the single-phase laminated perovskite structure potteries of six laminate structures, is under the condition of 100kV/cm measuring electric field, and remnant polarization is 1.35 ~ 2.61 μ C/cm
2, coercive field is 23 ~ 40kV/cm, is under the condition of 150kV/cm measuring electric field, remnant polarization is 4.99 ~ 7.48 μ C/cm
2, coercive field (2E
c) be 67 ~ 88kV/cm, under the normal temperature condition, the remanence rate is 1.12 ~ 2.60emu/g, coercive field (2H
c) be 250 ~ 360 Oe.
Description of drawings
Fig. 1 is the X-ray diffractogram of the laminated perovskite structure pottery that makes in the embodiment of the invention 1;
Fig. 2 is the stereoscan photograph of the laminated perovskite structure pottery that makes in the embodiment of the invention 1;
Fig. 3 is the ferroelectric properties survey sheet of the laminated perovskite structure pottery that makes in the embodiment of the invention 1;
Fig. 4 is the ferromagnetic property survey sheet of the laminated perovskite structure pottery that makes in the embodiment of the 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.
Therefore in the perovskite structure pottery because the oxygen room that the multivalence attitude of magnetic ion iron ion and bismuth element volatilize and cause easily causes 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 because the leakage current that the multivalence attitude of magnetic ion Fe causes; The not volatile rare earth element lanthanum ion that mixes in the A position can reduce the leakage current that volatilizees and increase because of bismuth ion, and the ferroelectric properties of laminated perovskite structure pottery is provided; At B position doping cobalt ion, iron and cobalt are the magnetic particle that has less than the 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, may further comprise the steps: A) titanate ester compound, bismuth source compound, lanthanum source compound, Fe source compound and cobalt source compound are dissolved in solvent in proportion, add the complexing agent mix and blend, after the pH value is adjusted to 5 ~ 7, the heating evaporate to dryness burns into powder, obtains powder after the pre-burning; B) with described powder compressing tablet, sintering obtains the 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: with the bismuth source compound, the 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 the complexing agent mix and blend, after the pH value is adjusted to 5 ~ 7, be preferably 6 ~ 7, obtain settled solution, the heating evaporate to dryness burns into powder, it is put to the retort furnace 700 ℃ ~ 800 ℃, after being preferably 720 ℃ ~ 780 ℃ 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 a kind of in Bismuth trinitrate, bismuth subnitrate, bismuth oxide, Bismuth Subcarbonate and the Oxalic acid bismuth salt, is preferably Bismuth trinitrate; Described lanthanum source compound is selected from a kind of in lanthanum nitrate, Phosbloc, lanthanum trioxide, lanthanum oxalate and the lanthanum acetate, is preferably lanthanum nitrate; Described Fe source compound is selected from a kind of in iron nitrate, ferric oxide, Z 250 and the 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 the 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 the glycine, the mol ratio of all metal ions is 1 ~ 2.5:1 in described complexing agent and the solution, be preferably 1.4 ~ 2:1,1.5 ~ 1.9:1 more preferably, described complexing agent is preferably ethylenediamine tetraacetic acid (EDTA) and citric acid, the mol ratio of all metal ions is 0.5 ~ 1.5:1:1 in itself and the solution, 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.
By burning into powder, can tentatively remove organic phase wherein among the present invention; Burn in step then can further be removed remaining carbon and nitrogen element, also is 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 all is 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.
The improvement Pechini method of carrying out is adopted in the preparation of powder in the described steps A in solution, compare with solid reaction process, the inventive method fully is 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 on the reactive behavior, and the Fe-Co ion fully is coupled, thereby obtains higher ferromagnetic property, and simultaneously, 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, need not directly to carry out sintering behind the compressing tablet through steps such as ball milling, pre-synthesis, plastic removals, 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: be the condition lower sheeting of 60 ~ 150MPa with described powder at pressure, be preferably 80 ~ 100MPa, obtain the cylindrical samples that thickness is 3 ~ 5mm, be preferably 4 ~ 5mm; Then described cylindrical samples is carried out sintering.Described hot pressed sintering or the retort furnace sintering of being sintered to is preferably hot pressed sintering, adopts hot pressed sintering can obtain the high-performance ceramic that the sintering degree is higher and density is higher under relatively low temperature, 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 ℃ ~ 1000 ℃, is preferably 800 ℃ ~ 950 ℃, and sintering time is 2 ~ 6h, is preferably 3 ~ 5h.
The concrete steps of described hot pressed sintering are: described cylindrical samples is placed 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 ℃ ~ 800 ℃; be preferably 650 ℃ ~ 750 ℃; be forced into 5 ~ 20MPa; be preferably 10 ~ 20MPa; extremely fully release behind 800 ℃ ~ 1000 ℃ insulations of the highest sintering temperature, 1 ~ 6h is preferably 3 ~ 5h, obtains the laminated perovskite structure pottery.Described protective atmosphere is protective atmosphere well known to those skilled in the art, is preferably in argon gas, oxygen and the nitrogen one or more.
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% among the above-mentioned steps A.So that the effect of a volatile element atmosphere sintering can be provided as protective layer with the surrounding layer of element, blocked in the sample element to non-with element surrounding layer ZrO
2The passage of powder or the diffusion of MgO powder can be protected the internal layer sample component, mainly is the accuracy of the cobalt element content of volatile bismuth element and easy diffusion, simultaneously, 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 the internal layer steps A, and difference only is the content of bismuth element.
Non-with element surrounding layer ZrO
2The effect of powder or MgO powder is to utilize its high-melting-point and high sintering temperature, reaches the purpose of isolation sample and mould, is convenient to the demoulding after the hot pressed sintering; The effect that it also has the thermal stresses buffering reaches the purpose of protecting sample and mould simultaneously.
In order to further specify 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.
Agents useful for same is commercially available in following examples, 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
1.1 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) are dissolved in the nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed in the crucible heating concentrated until the solution evaporate to dryness burns into powder, 750 ℃ of pre-burning 3h obtain powder in retort furnace.
1.2 be that cylindrical samples is made in dry-pressing under the condition of 80MPa at pressure with the powder that obtains in 1.1, sample size diameter 15mm, thickness 4mm, the cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder that obtains 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 with the cylindrical samples that obtains in 1.2, placing liner is ZrO
2In the corundum mould of powder protection, be under the atmosphere of 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 ℃, begin pressurization, behind 830 ℃, 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 the laminated perovskite structure pottery Bi of X-ray diffractometer (the Rigaku TTR III of Rigaku motor company type) to obtaining in 1.3
6LaFe
1.5Co
1.5Ti
3O
21Carry out structural analysis, obtain its X-ray diffractogram, as shown in Figure 1, the result shows, sample is the ceramics sample of single Aurivillius structure, does not have the existence of obvious second-phase.
Utilize the laminated perovskite structure pottery Bi of scanning electronic microscope (the JEOL JSM-6390LA of Jeol Ltd. type) to obtaining in 1.3
6LaFe
1.5Co
1.5Ti
3O
21Carry out morphology observation, obtain its stereoscan photograph, as shown in Figure 2, the result shows, its sintering degree is better, and the grain shape size is basically identical, and the thing pore exists, and the density of pottery is better.
Utilize the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 1.3 of ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type)
6LaFe
1.5Co
1.5Ti
3O
21Carry out ferroelectric properties test, obtain its ferroelectric properties survey sheet, as shown in Figure 3, the result shows, it is under the condition of 150kV/cm that pottery is measured electric field at normal temperature, remnant polarization (2P
r) be 7.48 μ C/cm
2, coercive field (2E
c) be 88kV/cm.
Utilize the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 1.3 of vibrating sample magnetometer (EV7 of U.S. ADE Co. type)
6LaFe
1.5Co
1.5Ti
3O
21Carry out the ferromagnetic property test, obtain its ferromagnetic property survey sheet, as shown in Figure 4, the result shows, the remanence rate (2M of pottery
r) be 1.12emu/g, coercive field (2H
c) be 360Oe.
2.1 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) are dissolved in the nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed in the crucible heating concentrated until the solution evaporate to dryness burns into powder, 750 ℃ of pre-burning 3h obtain powder in retort furnace.
2.2 be that cylindrical samples is made in dry-pressing under the condition of 80MPa at pressure with the powder that obtains in 2.1, sample size diameter 15mm, thickness 2mm, the cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder that obtains 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 the cylindrical samples with obtaining in 2.2 places retort furnace, is warming up to 950 ℃ in air atmosphere, behind the sintering 5h, obtains laminated perovskite structure pottery Bi
6LaFe
1.5Co
1.5Ti
3O
21
Utilize the laminated perovskite structure pottery Bi of ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type) to obtaining in 2.3
6LaFe
1.5Co
1.5Ti
3O
21Carry out at normal temperatures the ferroelectric properties test, obtain its ferroelectric properties, measuring electric field at normal temperature is under the condition of 150kV/cm, remnant polarization (2P
r) be 4.99 μ C/cm
2, coercive field (2E
c) be 67kV/cm.
Utilize the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 2.3 of vibrating sample magnetometer (EV7 of U.S. ADE Co. type)
6LaFe
1.5Co
1.5Ti
3O
21Carry out the ferromagnetic property test, obtain its ferromagnetic property, remanence rate (2M
r) be 1.93emu/g, coercive field (2H
c) be 344Oe.
3.1 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) are dissolved in the nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed in the crucible heating concentrated until the solution evaporate to dryness burns into powder, 750 ℃ of pre-burning 3h obtain powder in retort furnace.
3.2 be that cylindrical samples is made in dry-pressing under the condition of 80MPa at pressure with the powder that obtains in 3.1, sample size diameter 15mm, thickness 4mm, the cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder that obtains 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 with the cylindrical samples that obtains in 3.2, placing liner is ZrO
2In the corundum mould of powder protection, be under the atmosphere of 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 ℃, begin pressurization, behind 830 ℃, 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 the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 3.3 of ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type)
6.25La
0.75Fe
1.5Co
1.5Ti
3O
21Carry out the ferroelectric properties test, obtain its ferroelectric properties, measuring electric field at normal temperature is under the condition of 100kV/cm, remnant polarization (2P
r) be 2.61 μ C/cm
2, coercive field (2E
c) be 40kV/cm.
Utilize the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 3.3 of vibrating sample magnetometer (EV7 of U.S. ADE Co. type)
6.25La
0.75Fe
1.5Co
1.5Ti
3O
21Carry out the 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 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) are dissolved in the nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed in the crucible heating concentrated until the solution evaporate to dryness burns into powder, 750 ℃ of pre-burning 3h obtain powder in retort furnace.
4.2 be that cylindrical samples is made in dry-pressing under the condition of 80MPa at pressure with the powder that obtains in 4.1, sample size diameter 15mm, thickness 4mm, the cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder that obtains 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 with the cylindrical samples that obtains in 4.2, placing liner is ZrO
2In the corundum mould of powder protection, be under the atmosphere of 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 ℃, begin pressurization, behind 830 ℃, 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 the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 4.3 of ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type)
6.5La
0.5Fe
1.5Co
1.5Ti
3O
21Carry out the ferroelectric properties test, obtain its ferroelectric properties, measuring electric field at normal temperature is under the condition of 100kV/cm, remnant polarization (2P
r) be 1.53 μ C/cm
2, coercive field (2E
c) be 32kV/cm.
Utilize the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 4.3 of vibrating sample magnetometer (EV7 of U.S. ADE Co. type)
6.5La
0.5Fe
1.5Co
1.5Ti
3O
21Carry out the 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 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) are dissolved in the nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed in the crucible heating concentrated until the solution evaporate to dryness burns into powder, 750 ℃ of pre-burning 3h obtain powder in retort furnace.
5.2 be that cylindrical samples is made in dry-pressing under the condition of 80MPa at pressure with the powder that obtains in 5.1, sample size diameter 15mm, thickness 4mm, the cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder that obtains 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 with the cylindrical samples that obtains in 5.2, placing liner is ZrO
2In the corundum mould of powder protection, be under the atmosphere of 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 ℃, begin pressurization, behind 830 ℃, 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 the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 5.3 of ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type)
6.75La
0.25Fe
1.5Co
1.5Ti
3O
21Carry out the ferroelectric properties test, obtain its ferroelectric properties, measuring electric field at normal temperature is under the condition of 100kV/cm, remnant polarization (2P
r) be 1.89 μ C/cm
2, coercive field (2E
c) be 40kV/cm.
Utilize the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 5.3 of vibrating sample magnetometer (EV7 of U.S. ADE Co. type)
6.75La
0.25Fe
1.5Co
1.5Ti
3O
21Carry out the 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 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) are dissolved in the nitric acid, mix and blend, dripping ammoniacal liquor regulator solution pH value is 7, obtain settled solution, stablize 3h, be placed in the crucible heating concentrated until the solution evaporate to dryness burns into powder, 750 ℃ of pre-burning 3h obtain powder in retort furnace.
6.2 be that cylindrical samples is made in dry-pressing under the condition of 80MPa at pressure with the powder that obtains in 6.1, sample size diameter 15mm, thickness 4mm, the cylindrical samples skin is the surrounding layer of bismuth element excessive 10%, internal layer is the powder that obtains 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 with the cylindrical samples that obtains in 6.2, placing liner is ZrO
2In the corundum mould of powder protection, be under the atmosphere of 80:20 in the volume ratio of argon gas and oxygen, be warming up to 650 ℃, begin pressurization, behind 830 ℃, 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 the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 6.3 of ferroelectric properties survey meter (U.S. P-PMF of Radiant Technologies company type)
5.75La
1.25Fe
1.5Co
1.5Ti
3O
21Carry out the ferroelectric properties test, obtain its ferroelectric properties, measuring electric field at normal temperature is under the condition of 100kV/cm, remnant polarization (2P
r) be 1.35 μ C/cm
2, coercive field (2E
c) be 23kV/cm.
Utilize the at normal temperatures laminated perovskite structure pottery Bi to obtaining in 6.3 of vibrating sample magnetometer (EV7 of U.S. ADE Co. type)
5.75La
1.25Fe
1.5Co
1.5Ti
3O
21Carry out the ferromagnetic property test, obtain its ferromagnetic property, remanence rate (2M
r) be 1.64emu/g, coercive field (2H
c) be 290Oe.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (10)
1. 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.
2. the preparation method of a laminated perovskite structure pottery is characterized in that, may further comprise the steps:
A) 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 the complexing agent mix and blend, after regulating pH value to 5 ~ 7, the heating evaporate to dryness burns into powder, obtain powder after the pre-burning, wherein 0.2≤x≤1.5;
B) with described powder compressing tablet, sintering obtains the laminated perovskite structure pottery.
3. preparation method according to claim 2 is characterized in that, described bismuth source compound is selected from a kind of in Bismuth trinitrate, bismuth subnitrate, bismuth oxide, Bismuth Subcarbonate and the Oxalic acid bismuth salt.
4. preparation method according to claim 2 is characterized in that, described lanthanum source compound is selected from a kind of in lanthanum nitrate, Phosbloc, lanthanum trioxide, lanthanum oxalate and the lanthanum acetate.
5. preparation method according to claim 2 is characterized in that, described Fe source compound is selected from a kind of in iron nitrate, ferric oxide, Z 250 and the ironic oxalate.
6. preparation method according to claim 2 is characterized in that, described cobalt source compound is selected from a kind of in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt oxide, cobalt oxalate and the cobaltous acetate.
7. preparation method according to claim 2 is characterized in that, described complexing agent is selected from one or more in ethylenediamine tetraacetic acid (EDTA), citric acid and the glycine.
8. 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.
9. preparation method according to claim 2 is characterized in that, the temperature of described pre-burning is 700 ℃ ~ 800 ℃, and the time is 2 ~ 4h.
10. preparation method according to claim 2 is characterized in that, is sintered to hot pressed sintering or retort furnace sintering.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224392A (en) * | 2013-04-03 | 2013-07-31 | 中国科学技术大学 | Layered perovskite multiferroic material and preparation method thereof |
| CN105084888A (en) * | 2015-09-29 | 2015-11-25 | 中国科学技术大学 | Ceramic material and preparation method thereof |
| CN109516795A (en) * | 2018-11-28 | 2019-03-26 | 中国科学技术大学 | A kind of 0-3 ferrous acid bismuthino magnetic electric compound material and preparation method thereof |
| CN113492011A (en) * | 2020-04-07 | 2021-10-12 | 中国科学院化学研究所 | Method for removing Nitric Oxide (NO) by defect-containing perovskite material through photocatalysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768403A (en) * | 2003-02-27 | 2006-05-03 | Tdk株式会社 | Thin film capacity element composition, high-permittivity insulation film, thin film capacity element, thin film multilayer capacitor, electronic circuit and electronic apparatus |
| CN101704669A (en) * | 2009-11-27 | 2010-05-12 | 扬州大学 | Layered structure ferrotitanium lanthanum bismuth cobaltate ceramic with multiferroic and preparation method thereof |
-
2012
- 2012-09-29 CN CN201210375865.7A patent/CN102875146B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768403A (en) * | 2003-02-27 | 2006-05-03 | Tdk株式会社 | Thin film capacity element composition, high-permittivity insulation film, thin film capacity element, thin film multilayer capacitor, electronic circuit and electronic apparatus |
| CN101704669A (en) * | 2009-11-27 | 2010-05-12 | 扬州大学 | Layered structure ferrotitanium lanthanum bismuth cobaltate ceramic with multiferroic and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A. SRINIVAS ET AL.: "INVESTIGATION OF DIELECTRIC AND MAGNETIC NATURE OF Bi7Fe3Ti3O21", 《MATERIALS RESEARCH BULLETIN》 * |
| 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》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224392A (en) * | 2013-04-03 | 2013-07-31 | 中国科学技术大学 | Layered perovskite multiferroic material and preparation method thereof |
| CN105084888A (en) * | 2015-09-29 | 2015-11-25 | 中国科学技术大学 | Ceramic material and preparation method thereof |
| CN105084888B (en) * | 2015-09-29 | 2017-05-31 | 中国科学技术大学 | A kind of ceramic material and preparation method thereof |
| CN109516795A (en) * | 2018-11-28 | 2019-03-26 | 中国科学技术大学 | A kind of 0-3 ferrous acid bismuthino magnetic electric compound material and preparation method thereof |
| CN113492011A (en) * | 2020-04-07 | 2021-10-12 | 中国科学院化学研究所 | Method for removing Nitric Oxide (NO) by defect-containing perovskite material through photocatalysis |
| CN113492011B (en) * | 2020-04-07 | 2022-07-29 | 中国科学院化学研究所 | Method for removing Nitric Oxide (NO) by defect-containing perovskite material through photocatalysis |
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