CN102531595A - Preparation method for 0-3 compound multiple-ferrite ceramic of cobalt ferrite and lead lanthanum zironate titanate - Google Patents
Preparation method for 0-3 compound multiple-ferrite ceramic of cobalt ferrite and lead lanthanum zironate titanate Download PDFInfo
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Abstract
The invention relates to ferroelectric/ferromagnetic compound materials, in particular to a preparation method for 0-3 compound multiple-ferrite ceramic of cobalt ferrite and lead lanthanum zironate titanate, which is characterized in that lead lanthanum zironate titanate is used as a ferroelectric phase in multiple-ferrite ceramic, cobalt ferrite is used as a ferromagnetic phase in the multiple-ferrite ceramic, zirconium oxide sol is wrapped on the surface of the ferrite phase of the cobalt ferrite through sol-gel technology to form a zirconium dioxide coating layer through pyrolysis, 3-8% of LiBiO3 is added into the lead lanthanum zironate titanate to serve as low temperature sintering aid to perform low temperature sintering, the cobalt ferrite wrapped the zirconium dioxide on the surface is mixed with the lead lanthanum zironate titanate sintered at the low temperature according to the mass ratio of 0.1 to 0.5:1, and then mixture of the cobalt ferrite and the lead lanthanum zironate titanate are granulated, pressed and sintered to be prepared into compound ceramic. The preparation method enables CFO and lead lanthanum zironate titanate (PLZT) powder to be compounded and sintered, thereby being simple in process, low in cost and easy to achieve industrialized batch production.
Description
Technical field
The present invention relates to ferroelectric/ferromagnetic composite material, be specifically related to the preparation method of the compound many iron potteries of a kind of cobalt ferrite and lead lanthanum zirconate titanate 0-3.
Background technology
Have simultaneously that (instead) is ferroelectric, (instead) is ferromagnetic, the material of multiple character such as piezoelectricity is called multi-iron material; This type material gathers together electricity, magnetic, power; Can realize the regulation and control between these parameters; As can perhaps pass through the electropolarization of magnetic field control material, thereby make this type material in the novel electron device, important application prospects arranged through the magnetic of electric field controls material; For example: utilize magneto-electric coupledly, can change electropolarization through magnetic field, thereby change specific refractory power and the specific absorption of material, obtain controlled photomodulator to light; Non-volatile many iron storer through electric field and magnetic field write-read; The magnetic field modulation PZT; Utilize the magnetic field strength transducer of MS and piezoelectric effect etc.; The abundant physical content that is had at the potential application foreground of high-tech area and itself electricity, magnetic coupling mechanism just because of this many iron property electronic material; This type material has caused the great concern of industry member and academia, and has become forward position emerging in materialogy, physics and the chemical field and focus.
From last century the fifties end at Cr
2O
3Found in the monocrystalline since the magnetoelectric effect, the research of magnetoelectric material always extremely various countries scientific research institution pay attention to; Up to now, the material that contains magnetoelectric effect that it is found that has reached and has had more than hundreds of, can be divided into two big types in single-phase compound and matrix material substantially; Single-phase ferroelectric/the magneto-electric coupled coefficient of ferromagnetic material is lower usually, and only under far below the situation of room temperature, just has magnetoelectric effect, so can not meet requirement of actual application usually; The price of adding some materials is comparatively expensive; Complicated processing technology and under the alternation situation degeneration factor etc. of magnetoelectricity conversion performance; This make single-phase ferroelectric/progress of ferromagnetic material practical application is little always; Be to solve this difficult problem of practical application, people begin one's study ferroelectric/ferromagnetic composite material.
The preparation method of ferroelectric/ferromagnetic composite material bulk mainly contains Method for bonding (Guled laminated), polymer-based carbon method (Polymer-based), solid reaction process (Solid-state reaction) etc.; These materials are general because only realizing compound on macroscopical magnitude, so bulk has more defective, like macroscopic mechanical defect, disperse inequality, phase reaction, magneto-electric coupled coefficient low etc. mutually.
With ferromagnetic phase powder and ferroelectric phase powder, carry out solid state sintering at a certain temperature, obtained ferromagnetic/ferroelectric matrix material; Human solid reaction processes such as Mahajan have been prepared BaTiO
3/ CuFe
2O
4Ferromagnetic/ferroelectric the matrix material of structure, and obtained higher magneto-electric coupled coefficient
[1]People such as Dai also use the CuFe that this method has prepared the different volumes ratio
2O
4/ PbZr
0.53Ti
0.47O
4Ferroelectric/ferromagnetic composite material
[2]This kind method biggest advantage is that the experiment condition ratio is easier to control, and the cost of preparation is low, and is not easy to react between two phases; Sintering time, sintering temperature, heat-up rate, cooling rate can directly influence material microstructure and magnetoelectric effect, but the density of the prepared matrix material of this method, piezoelectric property and magnetoelectricity conversion performance have much room for improvement.
[1] R.P?Mahajan,?K.K?Patankar?and?S.A?Patil.?
Bull.?Mater.?Sci., 23 (2000),?p.?273；
[2] Y.R.?Dai,?P.?Bao,?J.S.?Zhu,?J.G.?Wan,?H.M.?Shen?and?J.M.?Liu.?
J.?Appl.?Phys., 96 (2004),?p.?5687。
Summary of the invention
This patent employing solid-phase sintering process prepares compound many iron potteries of high magnetoelectricity gain factor, with lead lanthanum zirconate titanate (Pb
1-1.5xLa
x(Zr
0.58Ti
0.42)
1-1.25yNb
yO
3+ 0.03 ~ 0.08wt% LiBiO
3(x=0.06, y=0.02); PLZT) as the ferroelectric phase in many iron pottery, with cobalt ferrite (CoFe
2O
4) as the ferromagnetic phase in many iron pottery, zirconia sol is coated on ferromagnetic phase cobalt ferrite (CoFe through sol-gel technology
2O
4) surface, form the zirconia-coated layer through pyrolysis, in PLZT, add the LiBiO of 3-8%
3Carry out low-temperature sintering as the low-temperature sintering auxiliary agent, then the surface is coated with the CoFe of ZIRCONIUM DIOXIDE 99.5
2O
4Mix with lead lanthanum zirconate titanate (PLZT) behind the sintering mass ratio, be prepared into composite ceramics through granulation, compressing tablet, sintering by 0.1-0.5:1.
Added low temperature component bismuthic acid lithium when preparing the ferroelectric phase in compound many iron pottery early stage, and bismuthic acid lithium addition is the 3-8% of PLZT quality, and 6% of preferred PLZT quality has reduced the sintering temperature of Pb-based lanthanumdoped zirconate titanates, has reduced biphase diffusion under the high temperature.
Coat dystectic zirconium white (2680 ℃ of fusing points) on the CFO surface; Because this one deck zirconium white can effectively stop the biphase ion diffusion when the composite ceramics sintering; Thereby blocked iron, cobalt ion diffusing, doping, prevented, the leakage conductance electric current when having reduced ceramic polarization because of the mix increase of the ferroelectric ceramic(s) phase dielectric loss that causes of iron, cobalt ion to the PLZT ferroelectric phase; Help the abundant polarization of sample, improved the piezoelectric property of composite ceramics.
The ZIRCONIUM DIOXIDE 99.5 layer at CFO and PLZT phase boundary place is extremely thin, has only the 0.25-0.35 micron, and the stress of the generation of the ferromagnetic phase magnetostrictive strain of CFO is directly delivered to the PLZT piezoelectric phase easily, helps improving the magnetoelectricity gain factor of material.
With CFO and the compound burning altogether of PLZT powder, technology is simple relatively, and cost is low, is easy to realize that industrial mass becomes to produce.
Description of drawings
The X ray diffracting spectrum of Fig. 1 differing temps sintering CFO/PLZT (3:7) pottery;
The different CFO/PLZT quality of Fig. 2 are than the X ray diffracting spectrum of composite ceramics;
The back scattering stereoscan photograph of Fig. 3 CFO/PLZT pottery section;
The element of Fig. 4 electronic scanning energy spectrum analysis distributes;
The different CFO/PLZT quality of Fig. 5 are than the impedance frequency spectrum of composite ceramics;
The impedance frequency spectrum of Fig. 6 differing temps sintering CFO/PLZT composite ceramics;
The ferroelectric hysteresis loop of Fig. 7 CFO/PLZT composite ceramics;
The magnetic hysteresis loop of Fig. 8 CFO/PLZT composite ceramics;
The magnetoelectricity gain factor of Fig. 9 composite ceramics is with the variation of biased magnetic field strength;
The magnetoelectricity gain factor of Figure 10 composite ceramics is with the variation of field frequency.
Embodiment
The preparation method of the compound many iron potteries of this high magnetoelectricity gain factor comprises following steps:
(1) PLZT powder preparing
Use analytically pure plumbous oxide, titanium oxide, ZIRCONIUM DIOXIDE 99.5, lanthanum sesquioxide, Niobium Pentxoxide to be raw material; Adopt traditional mixing oxidesintering technology, in 850 ℃ of pre-burnings 3 hours, (diameter was 3mm to pulverize back material powder and zirconia balls behind batch mixing; 5mm; The 10mm mass ratio is 4:2:1) by the mass ratio 1:4 nylon ball grinder of packing into, be medium mill 2 hours with water, obtain the PZT powder that median size is the 0.8-1.2 micron.
(2) CFO powder preparing
With Fe
2O
3With CoO 1:1 batch mixing in molar ratio, 850 ℃ of pre-burning 2h, 1275 ℃ of sintering 2h, CoFe
2O
4Powder is packed in the stainless cylinder of steel, and (diameter is respectively 2mm, 5mm to add the steel ball of 3-4 times of quality; The mass ratio of 8mm steel ball is 4:2:1), be medium with ethanol, with 300 rev/mins rotating speed ball millings 4 hours; Isolate slip, after 120 ℃ of oven dry, obtain the cobalt ferrite powder.
(3) the CFO surface coats ZIRCONIUM DIOXIDE 99.5 technology
The CFO powder is packed in the flask; The toluene that adds 10 times of CFO volumes; Ultra-sonic dispersion and stir 15 minutes after; Stir and to add zirconium iso-propoxide (mass ratio of CFO and zirconium iso-propoxide is 1:3 ~ 4) down, ultrasonic and stirred 30 minutes, (water: the ethanol mass ratio is 1:3 to dropping water/alcohol mixture under brute force stirs; Water: the zirconium iso-propoxide mol ratio is 7 ~ 10:1); Above-mentioned aaerosol solution backflow was steamed the part low-boiling point material in 30 minutes, cooling, suction filtration; Surface-coated zirconium white colloidal cobalt ferrite powder in 650 ℃ of pyrolysis 1 hour, is sieved after powder ground gently, classification, subsequent use.
(4) low-temperature sintering PLZT powder preparing
Bi (NO with charge calculation
3)
25H
2O puts into crucible and is dissolved in water, and treats to add load weighted PLZT powder after dissolving finishes, and stirs; The aqueous solution that adds LiAc again, Bi (NO
3)
25H
2The LiBiO that O and LiAc reaction generate
3Be 3 ~ 8% of PLZT powder quality, stirring heating, porphyrize behind evaporate to dryness; In 650 ° of C pyrolysis 1 hour, obtain the PZT powder of bismuthic acid lithium doping.
(5) CFO/PLZT Composite Preparation
Mass ratio by CFO:PLZT=0.1 ~ 0.5 mixes two kinds of powders; Z 150PH/(CFO+PLZT) 2% adding mass percentage concentration of solid masses ratio is 5% polyvinyl alcohol water solution according to adding; Obtain the compound many iron pottery of CFO/PLZT through granulation, compressing tablet sintering, sintering condition is: 1000 ℃-1150 ℃ sintering 15-60 minute.
Instance
With analytically pure plumbous oxide, titanium oxide, ZIRCONIUM DIOXIDE 99.5, lanthanum sesquioxide, Niobium Pentxoxide is raw material, prepares LiBiO by above-mentioned steps
3The CFO powder of doped P LZT and zirconia-coated.
Press mass ratio CFO:PLZT=1/9 respectively; 2/8,3/7 and 4/6 (volume ratio 14.4/85.6,27.4/72.6 and 39.3/60.7) mixes two kinds of powders; Add Z 150PH (5%) aqueous solution; Process diameter 11mm through granulation, compressing tablet, the disk of thickness 1.5mm obtained the composite ceramics disk in 15 minutes at 850-1150 ℃ of sintering; For the ease of comparing, the quality of all samples is identical with original size.
(1) PLZT powder preparing
Use analytically pure 127.77g plumbous oxide, 20.58g titanium oxide, 43.83g ZIRCONIUM DIOXIDE 99.5,6.15g lanthanum sesquioxide and 1.67g Niobium Pentxoxide to be raw material; Adopt traditional mixing oxidesintering technology, in 850 ℃ of pre-burnings 3 hours, (diameter was 3mm to pulverize back material powder and zirconia balls behind batch mixing; 5mm; The 10mm mass ratio is 4:2:1) by the mass ratio 1:4 nylon ball grinder of packing into, be medium mill 2 hours with water, obtaining median size is the PZT powder (Pb of 0.8-1.2 micron
0.91La
0.06(Zr
0.58Ti
0.42)
0.975Nb
0.02O
3).
(2) CFO powder preparing
With Fe
2O
3With CoO 1:1 batch mixing in molar ratio, 850 ℃ of pre-burning 2h, 1275 ℃ of sintering 2h, CoFe
2O
4Powder is packed in the stainless cylinder of steel, and (diameter is respectively 2mm, 5mm to add the steel ball of 3 times of quality; The mass ratio of 8mm steel ball is 4:2:1), be medium with ethanol, with 300 rev/mins rotating speed ball millings 4 hours; Isolate slip, after 120 ℃ of oven dry, obtain the cobalt ferrite powder.
(3) the CFO surface coats ZIRCONIUM DIOXIDE 99.5
The 8gCFO powder is packed in the flask, adds 25ml toluene, ultra-sonic dispersion and stir 15 minutes after, stir and add the 30g zirconium iso-propoxide down, ultrasonic and stirred 30 minutes, stir dropping 40g water/alcohol mixture down in brute force, water: the ethanol mass ratio is 1:3; Water: the zirconium iso-propoxide mol ratio is 7.19:1; Above-mentioned aaerosol solution backflow was steamed the part low-boiling point material in 30 minutes, cooling, suction filtration; Surface-coated zirconium white colloidal cobalt ferrite powder in 650 ℃ of pyrolysis 1 hour, is sieved after powder ground gently, classification, subsequent use.
(4) low-temperature sintering PLZT powder preparing
With 10.9g Bi (NO
3)
35H
2O puts into crucible and adds the suitable quantity of water dissolving, treats to add 94g PLZT powder after dissolving finishes, and stirs; Add 2.32g LiAc2H again
2The aqueous solution of O, Bi (NO
3)
35H
2O and LiAc2H
2The LiBiO that the O reaction generates
3Be 6% of PLZT powder quality, stirring heating, porphyrize behind evaporate to dryness; In 650 ° of C pyrolysis 1 hour, obtain the PZT powder of bismuthic acid lithium doping.
(5) CFO/PLZT Composite Preparation
10g CFO and two kinds of powders of 90gPLZT are mixed, and are 5% polyvinyl alcohol water solution according to adding the 40g mass concentration, obtain the compound many iron potteries of CFO/PLZT through granulation, compressing tablet sintering, and sintering condition is: 1000 ℃-1150 ℃ sintering 15-60 minute.
(1) PLZT powder preparing
Use analytically pure 127.77g plumbous oxide, 20.58g titanium oxide, 43.83g ZIRCONIUM DIOXIDE 99.5,6.15g lanthanum sesquioxide and 1.67g Niobium Pentxoxide to be raw material; Adopt traditional mixing oxidesintering technology, in 850 ℃ of pre-burnings 3 hours, (diameter was 3mm to pulverize back material powder and zirconia balls behind batch mixing; 5mm; The 10mm mass ratio is 4:2:1) by the mass ratio 1:4 nylon ball grinder of packing into, be medium mill 2 hours with water, obtaining median size is the PZT powder (Pb of 0.8-1.2 micron
0.91La
0.06(Zr
0.58Ti
0.42)
0.975Nb
0.02O
3).
(2) CFO powder preparing
With Fe
2O
3With CoO 1:1 batch mixing in molar ratio, 850 ℃ of pre-burning 2h, 1275 ℃ of sintering 2h, CoFe
2O
4Powder is packed in the stainless cylinder of steel, and (diameter is respectively 2mm, 5mm to add the steel ball of 3-4 times of quality; The mass ratio of 8mm steel ball is 4:2:1), be medium with ethanol, with 300 rev/mins rotating speed ball millings 4 hours; Isolate slip, after 120 ℃ of oven dry, obtain the cobalt ferrite powder.
(3) the CFO surface coats ZIRCONIUM DIOXIDE 99.5
8g CFO powder is packed in the flask, adds 25ml toluene, ultra-sonic dispersion and stir 15 minutes after, stir and add the 30g zirconium iso-propoxide down, ultrasonic and stirred 30 minutes, Dropwise 5 0g water/alcohol mixture under brute force stirs, water: the ethanol mass ratio is 1:3; Water: the zirconium iso-propoxide mol ratio is 8.98:1; Above-mentioned aaerosol solution backflow was steamed the part low-boiling point material in 30 minutes, cooling, suction filtration; Surface-coated zirconium white colloidal cobalt ferrite powder in 650 ℃ of pyrolysis 1 hour, is sieved after powder ground gently, classification, subsequent use.
(4) low-temperature sintering PLZT powder preparing
With 10.9g Bi (NO
3)
35H
2O puts into crucible and adds the suitable quantity of water dissolving, treats to add 94g PLZT powder after dissolving finishes, and stirs; Add 2.32g LiAc2H again
2The aqueous solution of O, Bi (NO
3)
35H
2O and LiAc2H
2The LiBiO that the O reaction generates
3Be 6% of PLZT powder quality, stirring heating, porphyrize behind evaporate to dryness; In 650 ° of C pyrolysis 1 hour, obtain the PZT powder of bismuthic acid lithium doping.
(5) CFO/PLZT Composite Preparation
20g CFO and two kinds of powders of 80gPLZT are mixed, and are 5% polyvinyl alcohol water solution according to adding the 40g mass concentration, obtain the compound many iron potteries of CFO/PLZT through granulation, compressing tablet sintering, and sintering condition is: 1000 ℃-1150 ℃ sintering 15-60 minute.
(1) PLZT powder preparing
Use analytically pure 127.77g plumbous oxide, 20.58g titanium oxide, 43.83g ZIRCONIUM DIOXIDE 99.5,6.15g lanthanum sesquioxide and 1.67g Niobium Pentxoxide to be raw material; Adopt traditional mixing oxidesintering technology, in 850 ℃ of pre-burnings 3 hours, (diameter was 3mm to pulverize back material powder and zirconia balls behind batch mixing; 5mm; The 10mm mass ratio is 4:2:1) by the mass ratio 1:4 nylon ball grinder of packing into, be medium mill 2 hours with water, obtaining median size is the PZT powder (Pb of 0.8-1.2 micron
0.91La
0.06(Zr
0.58Ti
0.42)
0.975Nb
0.02O
3).
(2) CFO powder preparing
With Fe
2O
3With CoO 1:1 batch mixing in molar ratio, 850 ℃ of pre-burning 2h, 1275 ℃ of sintering 2h, CoFe
2O
4Powder is packed in the stainless cylinder of steel, and (diameter is respectively 2mm, 5mm to add the steel ball of 3-4 times of quality; The mass ratio of 8mm steel ball is 4:2:1), be medium with ethanol, with 300 rev/mins rotating speed ball millings 4 hours; Isolate slip, after 120 ℃ of oven dry, obtain the cobalt ferrite powder.
(3) the CFO surface coats ZIRCONIUM DIOXIDE 99.5
8g CFO powder is packed in the flask, adds 25ml toluene, ultra-sonic dispersion and stir 15 minutes after, stir and add the 30g zirconium iso-propoxide down, ultrasonic and stirred 30 minutes, Dropwise 5 5g water/alcohol mixture under brute force stirs, water: the ethanol mass ratio is 1:3; Water: the zirconium iso-propoxide mol ratio is 9.88:1; Above-mentioned aaerosol solution backflow was steamed the part low-boiling point material in 30 minutes, cooling, suction filtration; Surface-coated zirconium white colloidal cobalt ferrite powder in 650 ℃ of pyrolysis 1 hour, is sieved after powder ground gently, classification, subsequent use.
(4) low-temperature sintering PLZT powder preparing
With 10.9g Bi (NO
3)
35H
2O puts into crucible and adds the suitable quantity of water dissolving, treats to add 94g PLZT powder after dissolving finishes, and stirs; Add 2.32g LiAc2H again
2The aqueous solution of O, Bi (NO
3)
35H
2O and LiAc2H
2The LiBiO that the O reaction generates
3Be 6% of PLZT powder quality, stirring heating, porphyrize behind evaporate to dryness; In 650 ° of C pyrolysis 1 hour, obtain the PZT powder of bismuthic acid lithium doping.
(5) CFO/PLZT Composite Preparation
30g CFO and two kinds of powders of 70gPLZT are mixed, and are 5% polyvinyl alcohol water solution according to adding the 40g mass concentration, obtain the compound many iron potteries of CFO/PLZT through granulation, compressing tablet, sintering, and sintering condition is: 1000 ℃-1150 ℃ sintering 15-60 minute.
With X-ray diffraction analysis the crystal phase structure of composite ceramics, the X-ray diffraction collection of illustrative plates of differing temps agglomerating composite ceramics sample when Fig. 1 is 3:7 for the CFO/PLZT mass ratio; Can find out the false cube corresponding characteristic diffraction peak of the spinel structure that comprises CFO in the collection of illustrative plates and PLZT, 28 ° with 35 ° near have two very little Jiao Lvshi diffraction peak mutually, this maybe be relevant with near the component variation the zirconia-coated layer; Fig. 2 is the X-ray diffraction collection of illustrative plates of the different CFO/PLZT quality of 1100 ℃ of agglomerating than composite ceramics sample, can find out: the characteristic diffraction peak with the raising spinel structure of CFO content strengthens gradually, and the diffraction peak of pyrochlore structure also increases gradually.
Analyze with ESEM behind the sample section economy-combat grinding and polishing light; Fig. 3 is the back scattering stereoscan photograph of CFO/PLZT pottery; There are three kinds of zones that color depth is different in sample; Each other boundary obviously, with the assay determination of electronics diffraction spectroscopy the element distribution of lead, zirconium, titanium, iron, cobalt, oxygen, like Fig. 4; Contrast through stereoscan photograph and distribution diagram of element can be found out: white for PLZT mutually, black is the CFO phase, grey is for being coated with zirconic cobalt ferrite.
Sample surfaces sintering silver electrode, at 4 kV/mm electric fields in room temperature 15 min that polarize.Short circuit is aging measured sample with electric impedance analyzer after 24 hours, and Fig. 5 is the frequency impedance spectrum of 1100 ℃ of sintered samples; Can find out the increase with CFO content, the radially resonance and the thickness resonance of sample all move to high frequency direction, and this mainly descends owing to the proportion that increases composite ceramics with CFO content; Fig. 6 is the impedance spectrum of differing temps sintering CFO/PLZT (3:7) composite ceramics; Raising along with sintering temperature; The resonance peak of composite ceramics strengthens and towards the high frequency direction action gradually, when surpassing 1100 ℃, because the leakage conductance of pottery increases; Ferroelectric phase is difficult to abundant polarization, and piezoelectric property reduces on the contrary; Calculate its electromechanical conversion coefficient, mechanical quality factor, frequency factor according to resonance-antiresonance; The capacitance of measure sample and dielectric loss, capacitance calculates its specific inductivity per sample, and its data are listed in table 1.
With the ferroelectric properties of the ferroelectric analyser measurement of LC material, Fig. 7 is the ferroelectric hysteresis loop of different CFO/PLZT mass ratioes and different sintering temperature gained samples, and can find out: sample has ferroelectric properties preferably; The uniform temp sintered sample shows that relatively residual polarization reduces with the minimizing of PLZT phase content; When the CFO/PLZT ratio was identical, the residual polarization of the less sample of CFO content increased with the raising of sintering temperature, and the residual polarization of the higher sample of CFO content increases earlier with the raising of sintering temperature; After reduce; Explain that the ZIRCONIUM DIOXIDE 99.5 layer can effectively stop and slow down the diffusion of ion such as leakage conductance such as height such as iron, cobalt grade to ferroelectric phase, but along with CFO content increases, total phase contact area increases; The high leakage conductance total ion concentration that gets into ferroelectric phase increases, and makes the ferroelectric phase performance degradation; ZIRCONIUM DIOXIDE 99.5 descended to the blocking capability of diffusion when in addition, temperature was higher than 1150 ℃.
Measured the magnetic property of sample with vibrating sample magnetometer, Fig. 8 is the magnetic hysteresis loop of 1100 ℃ of sintered samples, can find out that sample has typical ferromagnetic property, and saturation magnetization and residual magnetization all increase with the raising of CFO content.
The magnetoelectricity gain factor of composite ceramics sample was with the variation of biased magnetic field strength when Fig. 9 was 100kHz for frequency.Can find out: below 0.3 tesla; Magnetic field increases and two curves of magnetic field reduction process do not overlap; This is the difference of the front and back because ferromagnetic material is polarized; Measured curve overlaps fully after sample fully magnetizes in magnetic field, and direct current biasing magnetic field is not very big to the contribution of magnetoelectricity gain factor in addition, and this is very favourable in the application of magnetic field strength transducer and small power magnetoelectricity device to this material.
Figure 10 is the variation of the magnetoelectricity gain factor of composite ceramics sample with field frequency, and bias field is 0.6 tesla.Can find out: in the 100kHz scope, the magnetoelectricity gain factor increases with the increase of field frequency, and ferromagnetic phase ratio is high more; The magnetoelectricity gain factor is big more; The gain factor that to the CFO/PLZT mass ratio is 3/7 composite ceramics sample can reach 130mV/ (cm Oe), but when the CFO/PLZT mass ratio brings up to 4/6, the ferroelectricity deterioration of composite ceramics sample; Can't fully polarize, the magnetoelectricity gain factor diminishes.
The unit for electrical property parameters of table 1 CFO/PLZT composite ceramics
Claims (5)
1. the preparation method of the compound many iron potteries of cobalt ferrite and lead lanthanum zirconate titanate 0-3; It is characterized in that: with lead lanthanum zirconate titanate as the ferroelectric phase in many iron pottery; With cobalt ferrite as the ferromagnetic phase in many iron pottery; Through sol-gel technology zirconia sol is coated on ferromagnetic phase cobalt ferrite surface, forms the zirconia-coated layer, in lead lanthanum zirconate titanate, add the LiBiO of 3-8% through pyrolysis
3Carry out low-temperature sintering as the low-temperature sintering auxiliary agent, the lead lanthanum zirconate titanate after the cobalt ferrite that then surface is coated with ZIRCONIUM DIOXIDE 99.5 and the low-temperature sintering mixes by the mass ratio of 0.1-0.5:1, is prepared into composite ceramics through granulation, compressing tablet, sintering.
2. the preparation method of the compound many iron potteries of a kind of cobalt ferrite as claimed in claim 1 and lead lanthanum zirconate titanate 0-3; It is characterized in that: describedly zirconia sol is coated on ferromagnetic phase cobalt ferrite surface, forms zirconia-coated layer concrete steps through pyrolysis and be: in the flask that the cobalt ferrite powder is packed into, add the toluene of 10 times of CFO volumes through sol-gel technology; Ultra-sonic dispersion and stir 15 minutes after; Stir and to add zirconium iso-propoxide down, the mass ratio of cobalt ferrite powder and zirconium iso-propoxide is 1:3 ~ 4, and is ultrasonic and stirred 30 minutes; Under brute force stirs, drip water/alcohol mixture, water: the ethanol mass ratio is 1:3; Water: the zirconium iso-propoxide mol ratio is 7 ~ 10:1; Above-mentioned aaerosol solution backflow was steamed the part low-boiling point material in 30 minutes, cooling, suction filtration; Surface-coated zirconium white colloidal cobalt ferrite powder in 650 ℃ of pyrolysis 1 hour, is sieved after powder ground gently, classification, subsequent use.
3. the preparation method of the compound many iron potteries of a kind of cobalt ferrite as claimed in claim 1 and lead lanthanum zirconate titanate 0-3; It is characterized in that: the lead lanthanum zirconate titanate behind the described cobalt ferrite that the surface is coated with ZIRCONIUM DIOXIDE 99.5 and the sintering mixes by the mass ratio of 0.1-0.5:1; The concrete steps that are prepared into composite ceramics through granulation, compressing tablet, sintering are: the mass ratio 0.1-0.5:1 of the lead lanthanum zirconate titanate after the cobalt ferrite that is coated with ZIRCONIUM DIOXIDE 99.5 by the surface and the low-temperature sintering mixes two kinds of powders; It according to 2% adding mass percentage concentration of the cobalt ferrite that adds Z 150PH/be coated with ZIRCONIUM DIOXIDE 99.5 and the mass ratio of the lead lanthanum zirconate titanate after the low-temperature sintering 5% polyvinyl alcohol water solution; Obtain compound many iron pottery through granulation, compressing tablet sintering, sintering condition is: 1000 ℃-1150 ℃ sintering 15-60 minute.
4. the preparation method of the compound many iron potteries of a kind of cobalt ferrite as claimed in claim 1 and lead lanthanum zirconate titanate 0-3, it is characterized in that: described lead lanthanum zirconate titanate is Pb
0.91La
0.06(Zr
0.58Ti
0.42)
0.975Nb
0.02O
3
5. the preparation method of the compound many iron potteries of a kind of cobalt ferrite as claimed in claim 1 and lead lanthanum zirconate titanate 0-3, it is characterized in that: said bismuthic acid lithium addition is 6% of a lead lanthanum zirconate titanate quality.
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