CN1778761A - Softening method for producing ferroelectric and ferromagnetic composite material powder by home position - Google Patents
Softening method for producing ferroelectric and ferromagnetic composite material powder by home position Download PDFInfo
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- CN1778761A CN1778761A CN 200510086562 CN200510086562A CN1778761A CN 1778761 A CN1778761 A CN 1778761A CN 200510086562 CN200510086562 CN 200510086562 CN 200510086562 A CN200510086562 A CN 200510086562A CN 1778761 A CN1778761 A CN 1778761A
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Abstract
A soft chemical method for in-situ preparing powder with ferroelectric and ferromagnetic composite materials is carried out by adding ferrite metal nitrate and ferroelectric metal nitrate into citric acid solution, heating, stirring, adding into ferroelectric metal alkoxide, adjusting pH value, obtaining homogeneous and stable sol, preparing powder, drying the obtained precursor, baking, burning and heat treating the burnt powder to obtain the final powder. It is cheap and simple, and has better chemical evenness, high purity and fine particles.
Description
Technical field
The present invention relates to the preparation of ferroelectric-ferromagnetic functional materials, particularly relate to the softening method preparation and have magnetoelectric effect ferrite/ferroelectrics matrix material.
Background technology
Ferroelectric and ferromagnetic composite material is a kind of novel material with ferroelectric transition function, and it is by two kinds of monophase materialses--ferroelectric phase is composited through certain method mutually with ferromagnetic.The magnetoelectricity transition function of ferroelectric and ferromagnetic composite material is to realize that with ferromagnetic product effect mutually this product effect is magnetoelectric effect by ferroelectric phase.Because the special performance of ferroelectric-ferromagnetic matrix material, there is extensive and important purposes in fields such as its current measurement at microwave regime, ultra-high-tension power transmission line, wide band magnetic detection, magnetic sensors, and especially there are many outstanding advantages the accurate measurement aspect of electromagnetic exposure in microwave device, the high voltage electric delivery system.The ferroelectric-ferromagnetic composite study has caused various countries Materials science workers' attention.
Traditional ferroelectric-ferromagnetic block matrix material all is ferrite such as the Ni ferrite (NiFe that adopts solid phase method to prepare
2O
4), vectolite (CoFe
2O
4) and complex ferrite material and ferroelectrics such as Pb-based lanthanumdoped zirconate titanates (PZT), barium titanate (BaTiO
3) powder mixes then through high-energy ball milling that sintering forms, the ferroelectric-ferromagnetic two-phase can only be mixed on macro-scale like this, thereby has influenced the performance of coupling performance.Y.H.Tang etc. report in Materials Science andEngineering B 116 (2005) 150-155 and utilize solid phase method to prepare (1-x) CoFe
2O
4-xBa
0.55Sr
0.25Ca
0.2Nb
2O
6Matrix material, Fig. 3-9 are the SEM pattern of this matrix material, and as can be seen from the figure, the two-phase particle is all bigger, ferroelectric phase size-grade distribution inequality, and ferromagnetic being randomly dispersed in mutually in the middle of the ferroelectric phase can only reach mixing on macroscopic view.Xiwei Qi etc. report in Journalof Magnetism and MagneticMaterial 269 (2004) 352-358 and have prepared Ni with solid phase method
0.2Cu
0.2Zn
0.6Fe
1.96O
4-BaTiO
3Compound system, Figure 10 are the SEM pattern of this system, and compound system pattern that obtains as can be seen from the figure and Y.H Tang report are similar, also can only reach macroscopic and mix.
Existing chemical process prepares ferroelectric material such as barium titanate (BaTiO
3), Pb-based lanthanumdoped zirconate titanates (PZT) all is to adopt sol-gel method, is solvent with the ethylene glycol monoemethyl ether, because the ethylene glycol monoemethyl ether price comparison is high and toxic, so also restricted sol-gel process at industrial preparation ferroelectric material.
Summary of the invention
Purpose of the present invention mainly solves the problem of original ferroelectric and ferromagnetic composite material solid sintering technology macroscopic view mixing to coupling influence, and a kind of softening method of producing ferroelectric and ferromagnetic composite material powder by home position is provided.This method not only can guarantee that ferroelectric phase is coupled on micro-scale with ferromagnetic, thereby improves coupling performance, and the preparation method is simple, and is raw materials used all more common and cheap.
Realize that composite material powder preparation method of the present invention is as follows:
1, presoma preparation
By design requirements ferrite metal nitrate and ferroelectrics metal nitrate are joined in the aqueous citric acid solution, after stirring 1～2,60～80 ℃ of heating in water bath add ferroelectric metal alkoxide, after continuing to stir, add ammoniacal liquor and regulate pH value 6.5～7.5, restir obtained uniform and stable colloidal sol in 6～8 hours.Wherein the molar weight of citric acid is the molar weight summation of all nitrate nitrate radicals, and when nitrate radical molar weight during less than 5 times of metal alkoxide molar weights, the molar weight of institute's adding citric acid is 5 times of metal alkoxide molar weight.
2, powder preparing
Dry in 130～170 ℃ of loft drier prepared presoma, treat in 230～270 ℃ of loft drier, to toast again after moisture volatilizees fully, until burning, the later powder thermal treatment in 700～900 ℃ of retort furnaces of waiting to have burnt obtained the powder that needs in 1～2 hour.
Compared with prior art, because the present invention has adopted softening method, by adding aqueous citric acid solution, it is good to make the ferroelectric and ferromagnetic composite material powder of preparation have a chemical uniformity, the purity height, characteristics such as powder particle is thin, ferroelectric-ferromagnetic two are on good terms and reach mixing on the micro-scales of molecule rank even atomic level, thereby have guaranteed coupling performance.Solid sintering technology is normally carrying out sintering after the oxide compound of required constituent element or the mixing of carbonate process ball milling, this has just limited, and trace element mixes in the material preparation process, doping is too little, doped element can not uniform distribution in system, thereby influenced the doping effect, and softening method is having the incomparable advantage of solid phase method aspect the material doped modification, can realize the doping of any chemical dose.Present method has simple for process, raw materials used all more common and cheap characteristics.
Description of drawings
Fig. 1 represents 0.5Ni
0.5Co
0.028Zn
0.472Fe
2O
4-0.5Ba (Zr
0.05Ti
0.95) O
3900 ℃ of thermal treatment 120min of composite granule XRD synoptic diagram.
Fig. 2 represents 0.5Ni
0.5Co
0.028Zn
0.472Fe
2O
4-0.5Ba (Zr
0.05Ti
0.95) O
3900 ℃ of thermal treatment 120min of composite granule SEM synoptic diagram.
Fig. 3-Fig. 9 represents Y.H.Tang research (1-x) CoFe respectively
2O
4-xBa
0.55Sr
0.25Ca
0.2Nb
2O
6(x=0.2, x=0.4, x=0.5, x=0.6, x=0.7, x=0.8, x=0.9) the SEM pattern of matrix material.
Figure 10 represents Xiwei Qi research Ni
0.2Cu
0.2Zn
0.6Fe
1.96O
4-BaTiO
3Compound system
Embodiment
Embodiment 1:0.5Ni
0.5Co
0.028Zn
0.472Fe
2O
4-0.5Ba (Zr
0.05Ti
0.95) O
3Powder preparing
0.0125mol nickelous nitrate, 0.0007mol Xiao Suangu, 0.0118mol zinc nitrate, 0.025mol nitrate of baryta, 0.00125mol zirconium nitrate are joined in the 150g deionized water, add the 0.255mol citric acid again, stirred 2 hours at 70 ℃ of heating in water bath, the tetrabutyl titanate that slowly adds 0.02375mol again, wait to stir into after the homogeneous solution, add ammoniacal liquor and regulate PH=6.5, continue to stir the colloidal sol that formed stable uniform in 8 hours.Dry in 150 ℃ of loft drier prepared colloidal sol, treat in 250 ℃ of loft drier, to toast again moisture volatilizees fully after, until burning, the later powder sintering in 900 ℃ of retort furnaces of waiting to have burnt obtained the powder of needs in 1.5 hours.
Because nitrate radical molar weight summation is greater than 5 times of the metal alkoxide molar weight, the molar weight of citric acid is a nitrate radical molar weight summation.
Embodiment 2:0.2Ni
0.5Co
0.028Zn
0.472Fe
2O
4-0.8Ba (Zr
0.05Ti
0.95) O
3Powder preparing
The 0.19mol citric acid is joined in the 150g deionized water, add 0.005mol nickelous nitrate, 0.00028mol Xiao Suangu, 0.00472mol zinc nitrate, 0.04mol nitrate of baryta, 0.002mol zirconium nitrate again, stirred 2 hours at 75 ℃ of heating in water bath, the tetrabutyl titanate that slowly adds 0.038mol again, wait to stir into after the homogeneous solution, add ammoniacal liquor and regulate PH=7, continue to stir the colloidal sol that formed stable uniform in 7 hours.Dry in 140 ℃ of loft drier prepared colloidal sol, treat in 260 ℃ of loft drier, to toast again moisture volatilizees fully after, until burning, the later powder sintering in 850 ℃ of retort furnaces of waiting to have burnt obtained the powder of needs in 2 hours.
Because nitrate radical molar weight summation is less than 5 times of the metal alkoxide molar weight, the molar weight of citric acid is 5 times of the metal alkoxide molar weight.
Embodiment 3:0.5Ni
0.2Cu
0.2Zn
0.6Fe
2O
4-0.5Ba (Zr
0.05Ti
0.95) O
3Powder preparing
0.005mol nickelous nitrate, 0.005mol cupric nitrate, 0.015mol zinc nitrate, 0.025mol nitrate of baryta, 0.00125mol zirconium nitrate are joined in the 150g deionized water, add the 0.255mol citric acid again, stirred 2 hours at 80 ℃ of heating in water bath, the tetrabutyl titanate that slowly adds 0.02375mol again, wait to stir into after the homogeneous solution, add ammoniacal liquor and regulate PH=6.5, continue to stir the colloidal sol that formed stable uniform in 8 hours.Dry in 130 ℃ of loft drier prepared colloidal sol, treat in 250 ℃ of loft drier, to toast again moisture volatilizees fully after, until burning, the later powder sintering in 900 ℃ of retort furnaces of waiting to have burnt obtained the powder of needs in 2 hours.
Because nitrate radical molar weight summation is greater than 5 times of the metal alkoxide molar weight, the molar weight of citric acid is a nitrate radical molar weight summation.
0.5Ni as can be seen from Figure 1
0.5Co
0.028Zn
0.472Fe
2O
4-0.5Ba (Zr
0.05Ti
0.95) O
3System does not occur significantly diffusion mutually with this technology at 900 ℃ of 120min, ferroelectric phase and ferromagnetic independent respectively mutually the existence.There is not tangible two-phase region in the ferroelectric-ferromagnetic composite granule epigranular of Sheng Chenging as can be seen from Figure 2.
Claims (2)
1, a kind of softening method of producing ferroelectric and ferromagnetic composite material powder by home position is characterized in that, the step of preparation is:
1) presoma preparation
By design requirements ferrite metal nitrate and ferroelectrics metal nitrate are joined in the aqueous citric acid solution, after stirring 1～2,60～80 ℃ of heating in water bath add ferroelectric metal alkoxide, after continuing to stir, add ammoniacal liquor and regulate pH value 6.5～7.5, restir obtained uniform and stable colloidal sol in 6～8 hours;
2) powder preparing
Dry in 130～170 ℃ of loft drier prepared presoma, treat in 230～270 ℃ of loft drier, to toast again after moisture volatilizees fully, until burning, the later powder thermal treatment in 700～900 ℃ of retort furnaces of waiting to have burnt obtained the powder that needs in 1～2 hour.
2, the softening method of producing ferroelectric and ferromagnetic composite material powder by home position as claimed in claim 1, it is characterized in that, the molar weight of the citric acid that is added is the molar weight summation of all nitrate nitrate radicals, when nitrate radical molar weight during less than 5 times of metal alkoxide molar weights, the molar weight of institute's adding citric acid is 5 times of metal alkoxide molar weight.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398485C (en) * | 2006-09-20 | 2008-07-02 | 浙江大学 | Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic |
| CN101090024B (en) * | 2007-04-29 | 2010-12-15 | 湘潭大学 | La rear earth ion doped-bismuth titanate spinel ferrite ferroelectric ferromagnetic composite film preparation method |
| CN102093045A (en) * | 2010-12-01 | 2011-06-15 | 北京航空航天大学 | Barium titanate and barium ferrite composite powder with nucleus shell structure and preparation method thereof |
| CN103715487A (en) * | 2014-01-13 | 2014-04-09 | 中国科学院紫金山天文台 | Novel C-waveband miniaturized microwave isolator and application |
| CN109037435A (en) * | 2018-08-29 | 2018-12-18 | 郑州轻工业学院 | A kind of preparation method of the magnetoelectricity nanocomposite based on biological assisted self assembling |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225433C (en) * | 2002-06-10 | 2005-11-02 | 武汉理工大学 | New prepn process of ferroelectric-ferromagnetic functional complex in three-layer perovskite-like structure |
| CN1262514C (en) * | 2004-08-19 | 2006-07-05 | 南京大学 | Magnetoelectric composite film and its preparation method |
-
2005
- 2005-10-08 CN CNB2005100865623A patent/CN1317227C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398485C (en) * | 2006-09-20 | 2008-07-02 | 浙江大学 | Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic |
| CN101090024B (en) * | 2007-04-29 | 2010-12-15 | 湘潭大学 | La rear earth ion doped-bismuth titanate spinel ferrite ferroelectric ferromagnetic composite film preparation method |
| CN102093045A (en) * | 2010-12-01 | 2011-06-15 | 北京航空航天大学 | Barium titanate and barium ferrite composite powder with nucleus shell structure and preparation method thereof |
| CN103715487A (en) * | 2014-01-13 | 2014-04-09 | 中国科学院紫金山天文台 | Novel C-waveband miniaturized microwave isolator and application |
| CN109037435A (en) * | 2018-08-29 | 2018-12-18 | 郑州轻工业学院 | A kind of preparation method of the magnetoelectricity nanocomposite based on biological assisted self assembling |
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| CN1317227C (en) | 2007-05-23 |
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