CN101648813A - Method for improving ferroelectric property of single-phase multiferroic ceramic material - Google Patents
Method for improving ferroelectric property of single-phase multiferroic ceramic material Download PDFInfo
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- CN101648813A CN101648813A CN200910092385A CN200910092385A CN101648813A CN 101648813 A CN101648813 A CN 101648813A CN 200910092385 A CN200910092385 A CN 200910092385A CN 200910092385 A CN200910092385 A CN 200910092385A CN 101648813 A CN101648813 A CN 101648813A
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Abstract
The invention relates to a method for improving the ferroelectric property of a single-phase multiferroic ceramic material, which comprises the following steps: mixing Sc2O3 with high purity of 99.9 percent and Mn2O3 oxide powder according to the mol ratio of 1: 1, evenly grinding, primarily sintering under the condition of 900 DEG C, and keeping the temperature for 12 hours; evenly mixing and grinding the primarily-sintered mixture, then wrapping and encapsulating the mixture, keeping the temperature and the pressure for 15 minutes under the conditions of 5GPa and 1000 DEG C to synthesize a sample, and then quenching the sample to reach the room temperature and releasing the pressure; and carrying out low-temperature thermal treatment on the single-phase ScMnO3 ceramic sample prepared ina heating furnace under the O2 atmosphere at high pressure with the thermal temperature of 500 DEG C and the thermal treatment time of 12h. In the method, the high-compactness and single-phase multiferroic ceramic material ScMnO3 is prepared by adopting the high-temperature and high-pressure solid state reaction method, and then the low-temperature thermal treatment is carried out in the O2. Testsshow that the relative density of the material is more than 95 percent which is much more than the density about 70 percent of the sample prepared in the ordinary pressure, the electric resistance isgreatly increased, and better insulation property and ferroelectric property can be shown.
Description
Technical field
The present invention relates to a kind of method of improving ferroelectric property of single-phase multiferroic ceramic material.
Background technology
Single phase multi-iron material rare earth manganese oxide RMnO
3(R=Ho-Lu, Y and Sc), (spacer is P6 to have six side's perovskite structures
3Cm), each manganese atom is centered on formation MnO by three Sauerstoffatoms and two drift angle Sauerstoffatoms in the same plane
5The trigonal bipyramid body, each rare earth atom and seven Sauerstoffatoms link formation RO
7Polyhedron.Along the c axle, be total to the MnO on summit
5Bipyramid layer and the RO that is total to the limit
7Polyhedron layer stacking forms the stratiform sandwich structure near two-dimensional characteristics.The nearly two dimensional crystal structure of this uniqueness has caused ferroelectric appearance.Electrostatic effect and rare earth ion R
3+The MnO that causes of small-size effect
5The inclination of bipyramid, and huge R-O
PThe displacement that departs from symmetry centre is to bring out ferroelectric distored principal element.For such material, can utilize traditional high-temperature pressure solid reacting method to obtain, but the rare earth manganese oxide of this method preparation exists a lot of pores, defective etc., promptly the compactness of material is poor, insulating property are bad, are unfavorable for the ferroelectric properties of material is characterized.During research aspect carrying out ferroelectric properties, under effect of electric field, the sample of compactness difference can show bigger electric leakage problem, make us be difficult to obtain saturated ferroelectric hysteresis loop, and the dielectric loss value of material is also than traditional typical ferroelectrics BaTiO
3Ceramic is big many, and leakage current is the major cause that causes loss value excessive.Except the compactness extent of sample, the migration of oxygen room in the sample, and the grain boundary effect in the sample etc. also is the principal element that produces electric leakage.Therefore, seek the density that improves sample, the oxygen room in the minimizing sample and the method for grain boundary effect have great significance to improving the sample ferroelectric properties.
Summary of the invention
Problem at the prior art existence, the object of the present invention is to provide a kind of method of improving ferroelectric property of single-phase multiferroic ceramic material, this method utilizes the mode of High Temperature High Pressure to prepare high fine and close single-phase many iron stupalith, and, make the bill of material after the processing reveal better ferroelectric properties to its low-temperature heat treatment under oxygen atmosphere.
For achieving the above object, a kind of method of improving ferroelectric property of single-phase multiferroic ceramic material of the present invention is specially:
1) with 99.9% high-purity Sc
2O
3And Mn
2O
3Oxide powder is even with 1: 1 mixed in molar ratio, grinding, carries out preliminary sintering under 800-1000 ℃ condition, is incubated 12-48 hour;
2) mixture after will just burning carries out wrapping and encapsulating after evenly grinding, and carries out coming synthetic sample in heat-insulation pressure keeping 10-30 minute under 4-5Gpa, 900-1150 ℃ condition, then sample is quenched to room temperature, and release;
3) O in process furnace
2The single-phase ScMnO that under the atmosphere high pressure is prepared
3Ceramics sample is done low-temperature heat treatment, and heat treated temperature range is 300-600 ℃, and heat treatment time is 8-20 hour.
Further, the preliminary preferred temperature of agglomerating is 900 ℃ in the described step 1), and preferred soaking time is 12 hours.
Further, the preferred value of treatment condition is to carry out heat-insulation pressure keeping 15 minutes under 5Gpa, 1000 ℃ condition described step 2).
Further, heat treated preferred temperature is 500 ℃ in the described step 3), and preferred soaking time is 12 hours.
Further, described step 2) middle mixture is wrapped in the goldleaf, and is encapsulated in the boron nitride tube.
Further, described process furnace is graphite heater furnace or chamber type electric resistance furnace.
Further, described step 2) sample synthesizes on the big press of cubic apparatus and carries out in, is specially: at first carry out the demarcation of temperature and pressure, with the method control Heating temperature of control heating power; At room temperature slowly boost to 5GPa, restart heating schedule and be heated to 1000 ℃, insulation was quenched to room temperature after 15 minutes under high-temperature and high-pressure conditions, last slowly release.
The present invention has prepared single-phase many iron stupalith ScMnO of high densification with the High Temperature High Pressure solid reacting method
3, carry out low-temperature heat treatment in the oxygen then.Find by testing our, with the ScMnO of common constant-pressure and high-temperature method preparation
3Sample is compared, by high pressure method preparation and under 500 ℃ condition the relative density of heat treated sample surpass 95%, much larger than the sample rate about 70% of normal pressure preparation, resistance has also had very big increase, shows better insulativity and ferroelectric properties.
Description of drawings
Fig. 1 is the single-phase ScMnO of the present invention's preparation
3Sample and the ScMnO that under 500 ℃ of conditions, high pressure is prepared
3X-ray diffraction spectrum after the sample thermal treatment (XRD) collection of illustrative plates;
Fig. 2 a is the ScMnO of high-temperature pressure preparation of the present invention
3The scanning electron microscope of sample (SEM) figure;
Fig. 2 b is the ScMnO of High Temperature High Pressure preparation of the present invention
3The scanning electron microscope of sample (SEM) figure;
Fig. 3 is the single-phase ScMnO of High Temperature High Pressure preparation among the present invention
3The single-phase ScMnO of annealed in ceramics sample, the high pressure-temperature preparation back oxygen
3Ceramics sample, and the single-phase ScMnO of high-temperature pressure preparation
3The leakage current of ceramics sample is with the comparison of voltage change relation;
Fig. 4 a is the ScMnO of high-temperature pressure preparation of the present invention
3Sample carries out in the oxygen after the thermal treatment, the ferroelectric hysteresis loop figure under room temperature, electric field action;
Fig. 4 b is the ScMnO of High Temperature High Pressure preparation of the present invention
3Sample carries out in the oxygen after the thermal treatment, the ferroelectric hysteresis loop figure under room temperature, different electric field action.
Embodiment
Embodiment 1:
Utilize the high fine and close single-phase ScMnO of high temperature and high pressure method preparation
3Many iron ceramics sample.
(1) with 99.9% high-purity Sc
2O
3And Mn
2O
3Oxide powder is even with 1: 1 mixed in molar ratio, grinding, carries out preliminary sintering under 900 ℃ condition, is incubated 12 hours.
(2) be pressed into the sequin of diameter 5mm after the mixture after will just burning evenly grinds,, and progressively be encapsulated in boron nitride tube, the graphite heater furnace, carry out height in the high pressure assembly of packing at last and be pressed into the goldleaf parcel.Sample synthesizes on the big press of cubic apparatus and carries out, and at first carries out the demarcation of temperature and pressure before the High-Voltage Experimentation, with the method control Heating temperature of control heating power.Earlier at room temperature slowly boost to 5GPa, restart heating schedule and be heated to 1000 ℃, insulation was quenched to room temperature after 15 minutes under high-temperature and high-pressure conditions, last slowly release.
(3) with the single-phase ScMnO of High Temperature High Pressure synthetic
3Many iron samples carry out the low-temperature heat treatment of differing temps: in tube furnace, in oxygen atmosphere this sample is heat-treated under 500 ℃, heat treatment time is 12h.
Embodiment 2: utilize the high-temperature pressure solid reacting method to prepare single-phase ScMnO
3Many iron ceramics sample.
(1) with 99.9% high-purity Sc
2O
3And Mn
2O
3Oxide powder is even with 1: 1 mixed in molar ratio, grinding, in chamber type electric resistance furnace, carries out preliminary sintering under 900 ℃ the condition, insulation 24h.
(2) mix powder behind the preliminary sintering is milled evenly, be pressed into the sequin that diameter is 10mm with pressing machine, and then put into chamber type electric resistance furnace and carry out the abundant sintering second time, sintering condition is 1200 ℃, insulation 48h.
(3) with the single-phase ScMnO of high-temperature pressure synthetic
3Many iron samples carry out low-temperature heat treatment: in tube furnace, in oxygen atmosphere this sample is heat-treated under 500 ℃, heat treatment time is 12h.
As shown in Figure 1, high temperature and high pressure method involved in the present invention has all prepared purer single-phase ScMnO with solid reacting method traditional under the normal pressure
3Many iron ceramics sample.But the sample relative density of latter's preparation is lower, only reaches about 70%, and the sample rate of high temperature and high pressure method of the present invention preparation is up to 95%.From (shown in Fig. 2 a, Fig. 2 b) the photo of scanning electron microscope also as can be seen, arrange more loose between the particle of the sample that normal atmosphere sintering method obtains, there is more pore to exist, and the sample of high pressure method preparation has very high compactness, high-compactness is the prerequisite that obtains the high quality pottery, and helps to improve the ferroelectric properties of material.High temperature and high pressure all can make sample produce the oxygen room, thereby the oxygen room increases the electroconductibility generation leakage current of sample as producing electric charge carrier under the alive outside condition of charge defects.Leakage current is unfavorable for the acquisition of the ferroelectric signal of sample, therefore for the density of study sample and the migration of the oxygen room in the sample to the sample leakage current and to the influence of the ferroelectric test result of sample, we have provided the comparison of the leakage current of the sample after the anneal in that high pressure method, normal pressure method obtain and the oxygen with the voltage change relation, as shown in Figure 3.The insulating property of the sample of high pressure method preparation are better, and resistance is 2.33 * 10
10Bigger about 10 times than normal pressure-sintered sample resistance, the sample under the oxygen atmosphere after the thermal treatment is because the elimination in partial oxygen room has had largely the leakage current of sample and reduces, and sample shows better insulating property, and resistance is 5.12 * 10
10Shown in Fig. 4 a, Fig. 4 b, this figure has provided the comparison of the ferroelectric hysteresis loop after the sample thermal treatment of high-temperature pressure and high temperature and high pressure method preparation, and anneal makes ScMnO in high pressure method preparation and the oxygen atmosphere
3Showing of multi-iron material is better, more the ferroelectric properties of assertive evidence.
Claims (7)
1, a kind of method of improving ferroelectric property of single-phase multiferroic ceramic material is specially:
1) with 99.9% high-purity Sc
2O
3And Mn
2O
3Oxide powder is even with 1: 1 mixed in molar ratio, grinding, carries out preliminary sintering under 800-1000 ℃ condition, insulation 12-48h;
2) mixture after will just burning carries out wrapping and encapsulating after evenly grinding, and carries out heat-insulation pressure keeping 10-30 minute under 4-5Gpa, 900-1150 ℃ condition, comes synthetic sample, then sample is quenched to room temperature, and release;
3) O in process furnace
2The single-phase ScMnO that under the atmosphere high pressure is prepared
3Ceramics sample is done low-temperature heat treatment, and heat treated temperature range is 300-600 ℃, and heat treatment time is 8-20h.
2, the method for improving ferroelectric property of single-phase multiferroic ceramic material as claimed in claim 1 is characterized in that, the preliminary preferred temperature of agglomerating is 900 ℃ in the described step 1), and preferred soaking time is 12 hours.
3, the method for improving ferroelectric property of single-phase multiferroic ceramic material as claimed in claim 1 is characterized in that, described step 2) in the preferred value of treatment condition be under 5Gpa, 1000 ℃ condition, to carry out heat-insulation pressure keeping 15 minutes.
4, the method for improving ferroelectric property of single-phase multiferroic ceramic material as claimed in claim 1 is characterized in that, heat treated preferred temperature is 500 ℃ in the described step 3), and preferred soaking time is 12 hours.
5, the method for improving ferroelectric property of single-phase multiferroic ceramic material as claimed in claim 1 is characterized in that, mixture is wrapped in the goldleaf in the described step 2, and is encapsulated in the boron nitride tube.
6, the method for improving ferroelectric property of single-phase multiferroic ceramic material as claimed in claim 1 is characterized in that, described process furnace is graphite heater furnace or chamber type electric resistance furnace.
7, the method for improving ferroelectric property of single-phase multiferroic ceramic material as claimed in claim 1, it is characterized in that, described step 2) sample synthesizes on the big press of cubic apparatus and carries out in, is specially: at first carry out the demarcation of temperature and pressure, with the method control Heating temperature of control heating power; At room temperature slowly boost to 5GPa, restart heating schedule and be heated to 1000 ℃, insulation was quenched to room temperature after 15 minutes under high-temperature and high-pressure conditions, last slowly release.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891469A (en) * | 2010-04-30 | 2010-11-24 | 中国科学院物理研究所 | Method for regulating and controlling magnetic property and ferroelectric property of multiferroic material Bi2NiTiO6 |
| CN104425703A (en) * | 2013-08-29 | 2015-03-18 | 日立金属株式会社 | Piezoelectric film element, method of manufacturing piezoelectric film element, and electronic device using piezoelectric film element |
| CN106083035A (en) * | 2016-06-22 | 2016-11-09 | 刘和来 | A kind of piezoelectric acceleration transducer using nano barium phthalate ceramic standby |
| CN106116567A (en) * | 2016-06-22 | 2016-11-16 | 刘和来 | The preparation method of high density nano barium titanate titanate ceramics |
| CN106699168A (en) * | 2016-12-29 | 2017-05-24 | 陕西科技大学 | Method for preparing multiferroic composite ceramic |
-
2009
- 2009-09-11 CN CN200910092385A patent/CN101648813A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891469A (en) * | 2010-04-30 | 2010-11-24 | 中国科学院物理研究所 | Method for regulating and controlling magnetic property and ferroelectric property of multiferroic material Bi2NiTiO6 |
| CN101891469B (en) * | 2010-04-30 | 2012-09-05 | 中国科学院物理研究所 | Method for regulating and controlling magnetic property and ferroelectric property of multiferroic material Bi2NiTiO6 |
| CN104425703A (en) * | 2013-08-29 | 2015-03-18 | 日立金属株式会社 | Piezoelectric film element, method of manufacturing piezoelectric film element, and electronic device using piezoelectric film element |
| CN106083035A (en) * | 2016-06-22 | 2016-11-09 | 刘和来 | A kind of piezoelectric acceleration transducer using nano barium phthalate ceramic standby |
| CN106116567A (en) * | 2016-06-22 | 2016-11-16 | 刘和来 | The preparation method of high density nano barium titanate titanate ceramics |
| CN106083035B (en) * | 2016-06-22 | 2018-11-02 | 刘和来 | A kind of piezoelectric acceleration transducer standby using nano barium phthalate ceramic system |
| CN106116567B (en) * | 2016-06-22 | 2018-11-02 | 刘和来 | The preparation method of high density nano barium titanate titanate ceramics |
| CN106699168A (en) * | 2016-12-29 | 2017-05-24 | 陕西科技大学 | Method for preparing multiferroic composite ceramic |
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Application publication date: 20100217 |