CN110981466A - A layered magnetoelectric composite ceramic with enhanced interface coupling and preparation method thereof - Google Patents

A layered magnetoelectric composite ceramic with enhanced interface coupling and preparation method thereof Download PDF

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CN110981466A
CN110981466A CN201911211393.XA CN201911211393A CN110981466A CN 110981466 A CN110981466 A CN 110981466A CN 201911211393 A CN201911211393 A CN 201911211393A CN 110981466 A CN110981466 A CN 110981466A
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powder
sintering
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ferrite
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刘胜
颜铄清
邹鸿翔
贺君
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Hunan Institute of Engineering
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Abstract

一种界面耦合增强的层状磁电复合陶瓷及其制备方法，该层状磁电复合陶瓷由改性Bi0.5Na0.5TiO3基压电相和尖晶石铁氧体磁致伸缩相叠层共烧复合而成。本发明还包括所述复合磁电陶瓷的制备方法。本发明层状磁电复合陶瓷具有良好压电性能、磁致伸缩特性和高磁电电压系数，且制备工艺简单，性能稳定，环保无害，适用于磁电传感器、能量采集器和滤波器等电子器件领域。

Figure 201911211393

A layered magnetoelectric composite ceramic with enhanced interface coupling and a preparation method thereof, the layered magnetoelectric composite ceramic is composed of a modified Bi 0.5 Na 0.5 TiO 3 based piezoelectric phase and a spinel ferrite magnetostrictive phase stacked Co-fired composite. The present invention also includes the preparation method of the composite magnetoelectric ceramics. The layered magnetoelectric composite ceramic of the invention has good piezoelectric properties, magnetostrictive properties, high magnetoelectric voltage coefficient, simple preparation process, stable performance, environmental protection and harmlessness, and is suitable for magnetoelectric sensors, energy collectors, filters, etc. field of electronic devices.

Figure 201911211393

Description

Interface coupling enhanced layered magnetoelectric composite ceramic and preparation method thereof
Technical Field
The invention relates to a multifunctional composite ceramic material and a preparation method thereof, in particular to a layered magnetoelectric composite ceramic with enhanced interface coupling and a preparation method thereof.
Background
With the rapid development of information technology, a single functional material is difficult to meet the requirements of miniaturization and multi-functionalization of novel electronic components, and the development of multi-functional materials becomes a research hotspot. The magnetoelectric functional ceramic material not only has all the characteristics of a single ferroelectric material and a ferromagnetic material, but also has magnetoelectric effect generated by electric order and magnetic order coupling, so that the magnetoelectric functional ceramic material has wide application prospect in the fields of electronic materials and devices such as a magnetic or electric field sensor, a magnetoelectric storage unit, an energy acquisition device, a microwave device and the like.
The magnetoelectric functional ceramics can be roughly classified into three types, namely, a particle type, a layer type and a column type according to the composite structure type. Compared with a particle type and columnar type composite structure, the layered type magnetoelectric composite ceramic can avoid the problems of uneven dispersion of low-resistance phases in a matrix and leakage current caused by communication due to the laminated structure configuration; meanwhile, the direct co-firing combination of the phase interface can improve the stress transfer of the interface, and is beneficial to obtaining high magnetoelectric voltage coefficient and high magnetoelectric conversion efficiency, so that the material can play a unique role in the application field of novel intelligent magnetoelectric materials and devices as a magnetoelectric conversion unit or a sensitive element.
The interface coupling effect is one of the key factors for determining the magnetoelectric effect of the laminated magnetoelectric composite ceramic, and the improvement of the interface coupling strength of the piezoelectric layer and the magnetostrictive layer is very important. However, the problems of interface element diffusion and chemical reaction, interface microstructure defects, thermal shrinkage mismatch and the like easily occur in the high-temperature co-fired layered magnetoelectric ceramic, so that the interface stress transfer is weakened, and the generation of high magnetoelectric coupling coefficients is restricted. Although researchers have adopted methods such as reducing the co-firing temperature, doping modification, introducing a buffer layer and the like to improve the interface coupling effect in the co-firing process to a certain extent, the new problems such as low material density, abnormal grain growth at the interface and the like are easily caused, and the improvement of the magnetoelectric coupling performance of the layered magnetoelectric composite ceramic material is not facilitated.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the problems in the prior art and provides a layered magnetoelectric composite ceramic with enhanced interface coupling.
The invention aims to solve the second technical problem and provides a preparation method of the layered magnetoelectric composite ceramic.
The invention adopts the technical scheme that the layered magnetoelectric composite ceramic with enhanced interface coupling is prepared from Bi0.5Na0.5TiO3The base piezoelectric phase and the ferrite magnetostrictive phase are laminated and co-fired and compounded.
Preferably, the volume fraction of the ferrite magnetostrictive phase is 0.6-0.7.
Preferably, the piezoelectric phase is Bi0.5K0.5TiO3Modified Bi0.5Na0.5TiO3Of the formula Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3The value range of x is more than or equal to 0.18 and less than or equal to 0.2, the crystal structure is characterized by a structure with three-side and four-side phases coexisting, and a morphotropic phase boundary exists.
Preferably, the ferrite magnetostrictive phase is CoFe with a spinel structure2O4、Co0.6Zn0.4Fe2O4、NiFe2O4One kind of (1).
The invention adopts the technical scheme that the preparation method of the layered magnetoelectric composite ceramic for solving the second technical problem comprises the following steps:
(1) preparation of ferrite sol: adding water and a complexing agent into ferrite metal nitrate to obtain a mixed solution, adjusting the pH value, heating and stirring to obtain ferrite sol;
(2) preparation of ferrite powder: drying the ferrite sol obtained in the step (1), and fully burning the ferrite sol by using alcohol; pre-burning the powder formed after burning, grinding the powder into fine powder, adding a binder, uniformly mixing, pressing the mixture into a blank, heating the blank to remove the binder, sintering and cooling the blank to obtain block ceramic; crushing the block ceramic, and then performing ball milling to obtain ferrite powder;
(3) preparation of piezoelectric phase sol: adding water and a complexing agent into piezoelectric phase metal nitrate and n-butyl titanate to obtain a mixed solution, adjusting the pH value, heating and stirring to obtain piezoelectric phase sol;
(4) preparation of piezoelectric phase powder: drying the piezoelectric phase sol obtained in the step (3), fully burning the piezoelectric phase sol by using alcohol, pre-burning powder formed after burning, grinding the powder into fine powder, sintering and cooling to obtain piezoelectric phase powder;
(5) preparation of piezoelectric phase germ layer: adding a sintering aid and a binder into the piezoelectric phase powder obtained in the step (4), uniformly mixing, and pressing into a blank to obtain a piezoelectric phase germ layer;
(6) preparing layered magnetoelectric composite ceramic: and (3) adding a binder into the ferrite powder obtained in the step (2), uniformly stirring, pouring onto the piezoelectric phase germ layer obtained in the step (5), pressing into a laminated composite blank, heating to remove the binder, sintering, and cooling to obtain the laminated magnetoelectric composite ceramic.
Preferably, in step (1), the ferrite metal nitrate is nickel nitrate hexahydrate, cobalt nitrate hexahydrate, zinc nitrate hexahydrate or iron nitrate nonahydrate.
Preferably, in the step (1), the stirring time is 4-5 h, and the stirring speed is 500-950 r/min.
Preferably, in steps (1) and (3), the complexing agent is ethylenediaminetetraacetic acid and/or citric acid.
Preferably, in the steps (1) and (3), the molar ratio of the ethylenediamine tetraacetic acid to the citric acid is 4-3: 1.
Preferably, in the steps (1) and (3), the molar amount of the complexing agent is 1.1 to 1.2 times of the total molar amount of the cations in the mixed solution;
preferably, in the steps (1) and (3), the heating temperature is 85-95 ℃, and the heating time is 3.5-6 hours, preferably 4 hours;
preferably, in steps (1) and (3), the pH is neutral;
preferably, in the step (2), the drying temperature is 140-160 ℃, preferably 150 ℃, and the drying time is 3-5 h; preferably 4 h;
preferably, in the step (2), the pre-sintering temperature is 400-500 ℃, preferably 450 ℃, and the pre-sintering time is 1.5-3 hours, preferably 2 hours;
preferably, in the step (2), the sintering temperature is 1210-1250 ℃, and the sintering time is 4-6 h;
preferably, in the step (2), the medium for ball milling is absolute ethyl alcohol, and the grinding balls are two zirconia balls with the diameter of phi x 3mm and phi x 7mm, and the mass ratio of the two zirconia balls is 7-8: 3-2;
preferably, in the step (2), the ball-milling ball-material ratio is 10:1, and the ball-milling time is 6-8 h;
preferably, in steps (2), (5) and (6), the binder is polyvinyl alcohol;
preferably, in the steps (2), (5) and (6), the pressure for pressing into the blank is 60-80 Mpa;
preferably, in the steps (2) and (6), the heating and rubber discharging temperature is 500-650 ℃, preferably 550 ℃, and the heating and rubber discharging time is 20-45 min, preferably 30 min;
preferably, in the step (3), the piezoelectric phase metal nitrate is bismuth nitrate pentahydrate, potassium nitrate, sodium nitrate,
preferably, in the step (3), the ratio of the piezoelectric phase metal nitrate to bismuth in n-butyl titanate: sodium: potassium: the molar ratio of titanium is 1:1-x: x:2, and x is 0.18-0.2.
Preferably, in the step (3), the stirring time is 3-5 h, and the stirring rotation speed is 400-750 r/min;
preferably, in the step (4), the drying temperature is 105-135 ℃, preferably 120 ℃, and the drying time is 4.5-6 h;
preferably, in the step (4), the pre-sintering temperature is 400-500 ℃, preferably 450 ℃, and the pre-sintering time is 1.5-3 hours;
preferably, in the step (4), the sintering temperature is 1120-1150 ℃, and the sintering time is 2-3 h;
preferably, in the step (5), the sintering aid is Bi2O3And the amount of the sintering aid is 2-3% of the mass of the piezoelectric phase powder.
Preferably, in the step (6), the sintering temperature is 1070-1120 ℃, and the sintering time is 2-3 h.
According to the invention, a process of combining liquid phase sintering and grain refinement is adopted to compound the ceramic phase with high piezoelectric performance and large magnetostriction performance in a laminated manner, the bonding force between the piezoelectric layer and the magnetostriction layer is increased, the magnetoelectric coupling effect is strengthened, the interface in the prepared magnetoelectric laminated composite ceramic is tightly bonded, the microstructure defects such as obvious cracks or pores are avoided, the interface stress coupling is enhanced, the strong magnetic-electric coupling response is favorably generated, and the high magnetoelectric coupling coefficient is obtained.
Compared with the prior art, the invention has the following beneficial technical effects: the interface coupling enhanced layered magnetoelectric composite ceramic has high density, tight phase interface combination and no obvious structural defect; the piezoelectric ceramic has good piezoelectric performance, high saturation polarization intensity, high saturation magnetization intensity and large magnetostriction property; based on these physical properties, the material exhibits a strong magnetoelectric coupling effect; the preparation method is simple to operate, and the prepared material is stable in performance; the invention adopts Bi-containing oxide Bi2O3As a sintering aid, not only are impurity phase elements prevented from being introduced into the ferroelectric ceramic, but also Bi elements supplemented to a certain extent are volatilized in the high-temperature sintering process; the invention adopts modified lead-free Bi0.5Na0.5TiO3The base piezoelectric ceramic is environment-friendly, and reduces environmental pollution; meanwhile, the material has higher polarization strength and stronger piezoelectric response, and the electrical properties of the material can be controlled and adjusted through doping modification and process control so as to meet various application requirements; the invention adopts a process of combining liquid phase sintering and grain refinement, can solve the problem of mismatch of co-firing shrinkage of a magnetostrictive phase and a piezoelectric phase, increase the bonding force between the piezoelectric layer and the magnetostrictive layer and strengthen the magnetoelectric coupling effect; while reducing the powderThe granularity and the adoption of liquid phase sintering can reduce the sintering temperature of the ceramic, and have important significance for reducing energy consumption and saving cost.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of the layered magnetoelectric composite ceramic of the present invention, where 1 is a ferrite magnetostrictive phase and 2 is a piezoelectric phase.
FIG. 2 is a scanning electron micrograph of a cross section of the layered magnetoelectric composite ceramic according to example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of the layered magnetoelectric composite ceramic in example 1 of the present invention.
Fig. 4 is a raman spectrum of the layered magnetoelectric composite ceramic in example 1 of the present invention.
Fig. 5 is a hysteresis chart of the layered magnetoelectric composite ceramic in example 1 of the present invention.
Fig. 6 is a hysteresis chart of the layered magnetoelectric composite ceramic in example 1 of the present invention.
Fig. 7 is a graph showing the relationship between the magnetoelectric coupling coefficient of the layered magnetoelectric composite ceramic and the dc magnetic field in embodiment 1 of the present invention.
Fig. 8 is a graph showing the relationship between the magnetoelectric coupling coefficient of the layered magnetoelectric composite ceramic and the dc magnetic field in embodiment 2 of the present invention.
Fig. 9 is a graph showing the relationship between the magnetoelectric coupling coefficient of the layered magnetoelectric composite ceramic and the dc magnetic field in embodiment 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. Unless otherwise indicated, the chemicals used in the examples were all obtained from conventional commercial sources.
Example 1
The interface coupling of the embodiment is enhanced and the layered magnetoelectric composite ceramic is composed of piezoelectric phase Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3And ferrite CoFe2O4Composition, wherein x is 0.2, ferrite CoFe2O4Is 0.65.
The specific preparation process flow is as follows:
(1)CoFe2O4preparing sol: according to the Co: Fe chemical meterWeighing 14.55g of cobalt nitrate hexahydrate (with the purity of 98.5%) and 40.4g of ferric nitrate nonahydrate (with the purity of 98.5%) in a weight ratio of 1:2, dissolving in deionized water, adding 36.17g of ethylenediamine tetraacetic acid (with the purity of 98%) and 7.94g of citric acid (with the purity of 98%), and stirring to obtain a uniform mixed solution; then ammonia water is used for adjusting the pH value to be neutral, the prepared solution is placed in a water bath kettle with the constant temperature of 90 ℃ for heating, and stirring is carried out for 4 hours at the speed of 500r/min, so as to obtain stable and uniform CoFe2O4Sol;
(2)CoFe2O4preparation of powder: CoFe obtained in the step (1)2O4Putting the sol in a drying oven at 160 ℃, and drying for 3 hours to obtain fluffy black xerogel; fully burning the dried gel by alcohol to obtain coralline ashes; placing the ash substance powder in a box type resistance furnace, and presintering at 450 ℃ for 2 h; grinding, adding 2 wt% of polyvinyl alcohol, mixing uniformly, placing in a mould, and pressing under 60MPa to obtain a blank; then placing the formed blank in a box-type resistance furnace, preserving heat for 30min at 550 ℃, removing glue, then continuing heating to 1220 ℃ for sintering, wherein the sintering time is 5h, and furnace cooling is carried out to obtain CoFe2O4The block ceramic is put into a high-energy planetary ball mill for ball milling, the ball milling medium is absolute ethyl alcohol, the milling balls are zirconia balls with the diameter phi x 3mm and phi x 7mm, the mass ratio of the milling balls is 7:3, and the ball-to-material ratio is 10: 1; ball milling time is 8h, 10.83g CoFe is obtained2O4Powder;
(3)Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3preparing sol: weighing 12.13g of pentahydrate bismuth nitrate (with the purity of 98.5%), 0.51g of potassium nitrate (with the purity of 99%), 1.69g of sodium nitrate (with the purity of 99%) and 17.02g of n-butyl titanate (with the purity of 98%) according to the stoichiometric ratio of Bi to Na to K to Ti of 5:4:1:10, adding deionized water, 24.11g of ethylenediamine tetraacetic acid (with the purity of 98%) and 5.29g of citric acid (with the purity of 98%), and stirring to obtain a uniform mixed solution; then ammonia water is used for adjusting the pH value to be neutral, the obtained solution is placed in a water bath kettle with the constant temperature of 85 ℃, and the heating and stirring are carried out for 4 hours, so as to obtain stable and uniform Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Sol;
(4)Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3preparation of powder: bi obtained in the step (3)0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Drying the sol in a drying oven at 120 ℃ for 5 hours to obtain yellow-white xerogel; then, fully burning the dried gel by using alcohol to obtain coralline ashes; pre-sintering the ash powder at 450 ℃ for 2 h; grinding the pre-sintered powder, placing in a box-type resistance furnace, sintering at 1150 deg.C for 2h, and furnace cooling to obtain 10.02gBi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Powder;
(5)Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3preparation of germ layer: weighing 1.23g of Bi obtained in the step (4)0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Adding 0.025gBi into the powder2O3And 0.018g of polyvinyl alcohol, the mixture is evenly mixed and filled into a stainless steel model to prepare Bi under the pressure of 60MPa0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Germ layer;
(6) preparing layered magnetoelectric composite ceramic: weighing 2.03g of CoFe obtained in the step (2)2O4Adding 0.03g of polyvinyl alcohol into the powder, and uniformly stirring the mixture; then pouring the solution into Bi obtained in the step (5)0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Pressing the laminated composite blank body on the germ layer by using 60MPa pressure; taking out the blank, placing in a box-type resistance furnace, keeping the temperature at 550 ℃ for 30min for removing the glue, continuing to heat to 1100 ℃ after removing the glue, sintering for 2h, and cooling along with the furnace to obtain the layered magnetoelectric composite ceramic; in the sintering process, ferroelectric phase powder with the same composition and 2 times of mass is covered around the composite ceramic blank to be used as baking powder, so that the volatilization of bismuth in the sintering process is reduced.
The performance parameters of the layered magnetoelectric composite ceramic of the embodiment are shown in the following table:
Figure BDA0002295770940000061
as shown in fig. 1, the layered magnetoelectric composite ceramic of the present embodiment is composed of two layers, namely, a magnetostrictive layer and a piezoelectric layer;
as shown in fig. 2, the layered magnetoelectric composite ceramic of the embodiment has a compact microstructure, tight interlayer bonding, no obvious defects such as cracks, gaps and the like;
as shown in FIG. 3, the layered magnetoelectric composite ceramic of the present embodiment has a piezoelectric material Bi with a morphotropic phase boundary0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3And spinel ferrite CoFe2O4Composition, no impurity phase;
as shown in FIG. 4, the layered magnetoelectric composite ceramic of the present embodiment is composed of Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3And CoFe2O4Two phases are formed;
as shown in fig. 5 and fig. 6, the layered magnetoelectric composite ceramic of the present embodiment exhibits strong polarization and magnetization characteristics, which is helpful for generating a strong magnetoelectric coupling effect;
as shown in fig. 7, the layered magnetoelectric composite ceramic of the embodiment has a high magnetoelectric voltage coefficient, and can realize efficient conversion between magnetic energy and electric energy; the interface coupling coefficient of the composite ceramic is larger than 0.5 and far higher than that of a double-layer magnetoelectric composite material (generally between 0.2 and 0.4) prepared by bonding, and the composite ceramic shows good interface coupling effect.
Example 2
The interface coupling of the embodiment is enhanced and the layered magnetoelectric composite ceramic is composed of piezoelectric phase Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3And ferrite Co0.6Zn0.4Fe2O4Composition, wherein x is 0.2, ferrite Co0.6Zn0.4Fe2O4Is 0.7.
The specific preparation process flow is as follows:
(1)Co0.6Zn0.4Fe2O4preparing sol: according to the ratio of Co to Zn to FeWeighing 8.73g of cobalt nitrate hexahydrate (with the purity of 98.5%), 5.95g of zinc nitrate hexahydrate (with the purity of 98.5%) and 40.4g of ferric nitrate nonahydrate (with the purity of 98.5%) in a stoichiometric ratio of 3:2:10, dissolving in deionized water, adding 37.33g of ethylenediamine tetraacetic acid (with the purity of 98%) and 7.17g of citric acid (with the purity of 98%), and stirring to obtain a uniform mixed solution; then ammonia water is used for adjusting the pH value to be neutral, the obtained solution is placed in a water bath kettle with the constant temperature of 85 ℃ for heating, and stirring is carried out for 5 hours at the speed of 600r/min, so as to obtain stable and uniform Co0.6Zn0.4Fe2O4Sol;
(2)Co0.6Zn0.4Fe2O4preparation of powder: the Co obtained in the step (1) is treated0.6Zn0.4Fe2O4Drying the sol in a drying oven at 150 ℃ for 4h to obtain fluffy black xerogel; fully burning the dried gel by alcohol to obtain coralline ashes; placing the ash substance powder in a box type resistance furnace, pre-sintering at 450 ℃, and keeping the temperature for 3 h; grinding, adding 2 wt% of polyvinyl alcohol, mixing uniformly, placing in a mould, and pressing under 60MPa to obtain a blank; heating the formed blank in a box-type resistance furnace, keeping the temperature at 550 ℃ for 30min to remove the binder, continuously heating to 1220 ℃ to sinter for 5h, and cooling with the furnace to obtain Co0.6Zn0.4Fe2O4Bulk ceramic; mixing the obtained Co0.6Zn0.4Fe2O4Crushing the blocky ceramics, and placing the blocky ceramics into a high-energy planetary ball mill for ball milling, wherein the ball milling medium is absolute ethyl alcohol, and the grinding balls are zirconia balls with the diameter of phi x 3mm and phi x 7mm, the mass ratio of the balls to the materials is 8:2, and the ball-to-material ratio is 10: 1; ball milling time is 6h, 11.23g of Co is obtained0.6Zn0.4Fe2O4Powder;
(3)Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3preparing sol: weighing 12.13g of pentahydrate bismuth nitrate (with the purity of 98.5%), 0.51g of potassium nitrate (with the purity of 99%), 1.69g of sodium nitrate (with the purity of 99%) and 17.02g of n-butyl titanate (with the purity of 98%) according to the stoichiometric ratio of Bi to Na to K to Ti of 5:4:1:10, adding deionized water, 24.11g of ethylenediamine tetraacetic acid (with the purity of 98%) and 5.29g of citric acid (with the purity of 98%), stirring to obtain uniform mixtureMixing the liquid; then ammonia water is used for adjusting the pH value to be neutral, the obtained solution is placed in a water bath kettle with the constant temperature of 85 ℃, the heating and the stirring are carried out for 4 hours, and stable and uniform Bi is obtained0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Sol;
(4)Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3preparation of powder: bi obtained in the step (3)0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Drying the sol in a drying oven at 120 ℃ for 5 hours to obtain yellow-white xerogel; fully burning the dried gel by alcohol to obtain coralline ashes; pre-burning the ash powder at 450 ℃ for 2 h; grinding the pre-sintered powder, placing the powder into a box-type resistance furnace, sintering the powder for 2 hours at 1150 ℃, and cooling the powder along with the furnace to obtain 10.02g of Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Powder;
(5)Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3preparation of germ layer: weighing 1.05g of Bi obtained in the step (4)0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Pulverizing, adding 0.032gBi2O3And 0.016g of polyvinyl alcohol, mixing uniformly, filling into a stainless steel mold, and preparing into germ layers under the pressure of 60MPa to obtain Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3Germ layer;
(6) preparing the layered composite ceramic: weighing 2.19g of Co obtained in step (2)0.6Zn0.4Fe2O4Adding 0.032g of polyvinyl alcohol into the powder, and uniformly stirring; then pouring the solution into Bi obtained in the step (5)0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3On the germ layer, the laminated composite embryo body is pressed by using 60MPa pressure; taking out the blank, placing in a box-type resistance furnace, keeping the temperature at 550 ℃ for 30min for removing the glue, continuing to heat to 1070 ℃ after removing the glue, sintering for 2h, and cooling along with the furnace to obtain the layered magnetoelectric composite ceramic. In the sintering process, the composite ceramic blank is covered with the same group at the peripheryThe ferroelectric phase powder with 2 times of mass is used as baking powder to reduce the volatilization of bismuth in the sintering process.
The performance parameters of the layered magnetoelectric composite ceramic of the embodiment are shown in the following table:
Figure BDA0002295770940000081
as shown in fig. 8, the layered magnetoelectric composite ceramic of the embodiment has a high magnetoelectric voltage coefficient, the maximum magnetoelectric voltage coefficient reaches 85.02(mV/cm · Oe), and efficient conversion of magnetic energy and electric energy can be realized; the interface coupling coefficient of the composite ceramic is far higher than that of a double-layer magnetoelectric composite material (generally between 0.2 and 0.4) prepared by bonding, and the good interface coupling effect is displayed.
Example 3
The interface coupling of the embodiment is enhanced and the layered magnetoelectric composite ceramic is composed of piezoelectric phase Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3And ferrite NiFe2O4Composition, wherein x is 0.18, ferrite NiFe2O4Is 0.67.
The specific preparation process flow is as follows:
(1)NiFe2O4preparing sol: weighing 14.53g of nickel nitrate hexahydrate (with the purity of 98.5%) and 40.4g of ferric nitrate nonahydrate (with the purity of 98.5%) according to the stoichiometric ratio of Ni to Fe of 1:2, dissolving in deionized water, adding 36.82g of ethylenediamine tetraacetic acid (with the purity of 98%) and 8.01g of citric acid (with the purity of 98%), and stirring to obtain a uniform mixed solution; then ammonia water is used for adjusting the pH value to be neutral, the prepared solution is placed in a water bath kettle with the constant temperature of 90 ℃ for heating, and stirring is carried out for 4h at the speed of 700r/min, so as to obtain stable and uniform NiFe2O4Sol;
(2)NiFe2O4preparation of powder: NiFe obtained in the step (2)2O4Drying the sol in a drying oven at 150 ℃ for 4h to obtain fluffy black xerogel; fully burning the dried gel by alcohol to obtain coralline ashes; placing the ash substance powder in a box type resistance furnace, and presintering at 450 ℃ for 2 h; after grinding, adding2 wt% of polyvinyl alcohol is mixed and placed in a mould to be pressed into a blank under the pressure of 60 MPa; heating the formed blank in a box-type resistance furnace, maintaining the temperature at 550 ℃ for 30min to remove the binder, continuously heating to 1250 ℃ to sinter for 4h, and furnace-cooling to obtain NiFe2O4Bulk ceramic; the obtained NiFe2O4Crushing the blocky ceramics, and placing the blocky ceramics into a high-energy planetary ball mill for ball milling, wherein the ball milling medium is absolute ethyl alcohol, and the grinding balls are zirconia balls with the diameter of phi x 3mm and phi x 7mm, the mass ratio of the grinding balls is 7:3, and the ball-to-material ratio is 10: 1; ball milling for 6h to obtain 10.99g of NiFe2O4Powder;
(3)Bi0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3preparing sol: weighing 12.13g of pentahydrate bismuth nitrate (with the purity of 98.5%), 0.45g of potassium nitrate (with the purity of 99%), 1.74g of sodium nitrate (with the purity of 99%) and 17.02g of n-butyl titanate (with the purity of 98%) according to the stoichiometric ratio of Bi to Na to K to Ti of 50:41 to 9:100, adding deionized water, 24.11g of ethylenediamine tetraacetic acid (with the purity of 98%) and 5.29g of citric acid (with the purity of 98%), and stirring to obtain a uniform mixed solution; then ammonia water is used for adjusting the pH value to be neutral, the solution is placed in a water bath kettle with the constant temperature of 85 ℃, and the solution is heated and stirred for 4 hours to obtain stable and uniform Bi0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3Sol;
(4)Bi0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3preparation of powder: bi obtained in the step (3)0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3Drying the sol in a drying oven at 120 ℃ for 5 hours to obtain yellow-white xerogel; fully burning with alcohol to obtain coral-shaped ashes; pre-sintering the ash powder at 450 ℃ for 2 h; grinding the pre-sintered powder, placing the powder into a box-type resistance furnace, sintering the powder for 2 hours at 1150 ℃, and cooling the powder along with the furnace to obtain 9.88g of Bi0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3Powder;
(5)Bi0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3preparation of germ layer: weighing 1.15g of Bi obtained in the step (5)0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3Powder, adding 0.034g Bi2O3And 0.017g of polyvinyl alcohol are mixed evenly and filled into a stainless steel model to be made into germ layers under the pressure of 60MPa to obtain Bi0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3Germ layer;
(6) preparing the layered composite ceramic: weighing 2.11g of NiFe obtained in the step (2)2O4Adding 0.03g of polyvinyl alcohol into the powder, and uniformly stirring; then pouring the solution into Bi obtained in the step (5)0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3On the germ layer, the laminated composite embryo body is pressed by using 60MPa pressure; taking out the blank, placing in a box-type resistance furnace, keeping the temperature at 550 ℃ for 30min for removing the glue, continuing to heat to 1080 ℃ for sintering after removing the glue, wherein the sintering time is 2h, and cooling along with the furnace to obtain the layered magnetoelectric composite ceramic. In the sintering process, ferroelectric phase powder with the same composition and 2 times of mass is covered around the composite ceramic blank to be used as baking powder, so that the volatilization of bismuth in the sintering process is reduced.
The performance parameters of the layered magnetoelectric composite ceramic of the embodiment are shown in the following table:
Figure BDA0002295770940000101
as shown in fig. 9, the layered magnetoelectric composite ceramic of the embodiment has a high magnetoelectric voltage coefficient, the maximum magnetoelectric voltage coefficient is as high as 105.41mV/cm · Oe, and the high-efficiency conversion of magnetism and electric energy can be realized; the interface coupling coefficient of the composite ceramic is far higher than that of a double-layer magnetoelectric composite material (generally between 0.2 and 0.4) prepared by bonding, and the good interface coupling effect is displayed.

Claims (10)

1.一种界面耦合增强的层状磁电复合陶瓷，其特征在于，该复合陶瓷由Bi0.5Na0.5TiO3基压电相和铁氧体磁致伸缩相叠层共烧复合而成。1. A layered magnetoelectric composite ceramic with enhanced interface coupling, characterized in that the composite ceramic is composed of Bi 0.5 Na 0.5 TiO 3 based piezoelectric phase and ferrite magnetostrictive phase stacked and co-fired. 2.根据权利要求1所述层状磁电复合陶瓷，其特征在于，所述铁氧体磁致伸缩相的体积分数为0.6~0.7。2 . The layered magnetoelectric composite ceramic according to claim 1 , wherein the volume fraction of the ferrite magnetostrictive phase is 0.6-0.7. 3 . 3.根据权利要求1或2所述层状磁电复合陶瓷，其特征在于，所述Bi0.5Na0.5TiO3基压电相为Bi0.5K0.5TiO3改性Bi0.5Na0.5TiO3，其分子式为Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3，x取值范围为0.18≤x≤0.2，其晶体结构特征为三方和四方相共存的结构，存在准同型相界。3. The layered magnetoelectric composite ceramic according to claim 1 or 2, wherein the Bi 0.5 Na 0.5 TiO 3 based piezoelectric phase is Bi 0.5 K 0.5 TiO 3 modified Bi 0.5 Na 0.5 TiO 3 . The molecular formula is Bi 0.5 Na 0.5 TiO 3 - x Bi 0.5 K 0.5 TiO 3 , the value of x is in the range of 0.18≤x≤0.2 , and its crystal structure is characterized by the coexistence of trigonal and tetragonal phases, and there is a quasi-isotype phase boundary. 4.根据权利要求1~3之一所述层状磁电复合陶瓷，其特征在于，所述铁氧体磁致伸缩相为尖晶石结构CoFe2O4、Co0.6Zn0.4Fe2O4、NiFe2O4中的一种。4 . The layered magnetoelectric composite ceramic according to claim 1 , wherein the ferrite magnetostrictive phase is spinel structure CoFe 2 O 4 , Co 0.6 Zn 0.4 Fe 2 O 4 . , one of NiFe 2 O 4 . 5.一种如权利要求1~4之一所述层状磁电复合陶瓷的制备方法，包括以下步骤：5. A method for preparing layered magnetoelectric composite ceramics as described in one of claims 1 to 4, comprising the following steps: （1）铁氧体溶胶的制备：将铁氧体金属硝酸盐加入水、络合剂，得混合液，调节pH值，加热，搅拌，得铁氧体溶胶；(1) Preparation of ferrite sol: adding ferrite metal nitrate to water and a complexing agent to obtain a mixed solution, adjusting the pH value, heating and stirring to obtain a ferrite sol; （2）铁氧体粉末的制备：将步骤（1）所得铁氧体溶胶干燥，并用酒精充分燃烧；将燃烧后形成的粉末进行预烧，再研磨成细粉，加入粘结剂，混合均匀，压制成胚，加热排胶，烧结，冷却，得块体陶瓷；将块体陶瓷破碎，再球磨，得铁氧体粉末；(2) Preparation of ferrite powder: the ferrite sol obtained in step (1) is dried and fully burned with alcohol; the powder formed after burning is pre-fired, then ground into fine powder, added with a binder, and mixed evenly , pressed into embryos, heated and degummed, sintered, and cooled to obtain block ceramics; crushed block ceramics, and then ball-milled to obtain ferrite powder; （3）压电相溶胶的制备：将压电相金属硝酸盐及钛酸正丁酯加入水、络合剂，得混合液，调节pH值，加热，搅拌，得压电相溶胶；(3) Preparation of piezoelectric phase sol: adding piezoelectric phase metal nitrate and n-butyl titanate to water and complexing agent to obtain a mixed solution, adjusting pH value, heating and stirring to obtain piezoelectric phase sol; （4）压电相粉体的制备：将步骤（3）所得压电相溶胶干燥，并用酒精充分燃烧，将燃烧后形成的粉末进行预烧，再研磨成细粉，然后进行烧结，冷却，得压电相粉体；(4) Preparation of piezoelectric phase powder: the piezoelectric phase sol obtained in step (3) is dried, and fully burned with alcohol, the powder formed after the combustion is pre-fired, and then ground into fine powder, and then sintered, cooled, Obtain piezoelectric phase powder; （5）压电相胚层的制备：向步骤（4）所得压电相粉体中加入烧结助剂和粘结剂，混合均匀，压制成胚，得压电相胚层；(5) Preparation of piezoelectric phase germ layer: adding sintering aids and binders to the piezoelectric phase powder obtained in step (4), mixing uniformly, and pressing into embryos to obtain piezoelectric phase germ layer; （6）层状磁电复合陶瓷的制备：向步骤（2）所得铁氧体粉末中加入粘结剂，搅拌均匀，然后倒至步骤（5）所得压电相胚层上，压制成叠层复合胚体，加热排胶，再进行烧结，冷却，即得层状磁电复合陶瓷。(6) Preparation of layered magnetoelectric composite ceramics: add a binder to the ferrite powder obtained in step (2), stir evenly, and then pour it onto the piezoelectric phase germ layer obtained in step (5), and press it into a laminated composite The embryo body is heated and degummed, and then sintered and cooled to obtain a layered magnetoelectric composite ceramic. 6.根据权利要求5所述层状磁电复合陶瓷的制备方法，其特征在于，步骤（1）中，所述铁氧体金属硝酸盐为六水合硝酸镍、六水合硝酸钴、六水合硝酸锌、九水合硝酸铁，所述搅拌的时间为3~5h，所述搅拌的转速为500~950 r/min。The method for preparing layered magnetoelectric composite ceramics according to claim 5, wherein in step (1), the ferrite metal nitrate is nickel nitrate hexahydrate, cobalt nitrate hexahydrate, nitric acid hexahydrate Zinc and ferric nitrate nonahydrate, the stirring time is 3~5h, and the stirring speed is 500~950 r/min. 7.根据权利要求5或6所述层状磁电复合陶瓷的制备方法，其特征在于，步骤（1）和（3）中，所述络合剂为乙二胺四乙酸和/或柠檬酸，乙二胺四乙酸与柠檬酸的摩尔比为4~3:1，所述络合剂的摩尔量为混合液中阳离子总摩尔量的1.1~1.2倍，所述pH值为中性；所述加热的温度优选为85~95℃，加热的时间优选为3.5~6h。7. The method for preparing layered magnetoelectric composite ceramics according to claim 5 or 6, wherein in steps (1) and (3), the complexing agent is ethylenediaminetetraacetic acid and/or citric acid , the molar ratio of EDTA and citric acid is 4~3:1, the molar amount of the complexing agent is 1.1~1.2 times of the total molar amount of cations in the mixed solution, and the pH value is neutral; The heating temperature is preferably 85~95°C, and the heating time is preferably 3.5~6h. 8.根据权利要求5~7之一所述层状磁电复合陶瓷的制备方法，其特征在于，步骤（2）中，所述干燥的温度为140~160℃，优选150℃，干燥的时间为3~5h；所述预烧的温度为400~500℃，预烧的时间为1.5~3h；所述烧结温度为1210~1250℃，烧结时间为4~6h；所述球磨的介质优选为无水乙醇，磨球为直径优选Φ×3mm和Φ×7mm两种氧化锆球，两者质量配比优选为7~8:3~2；所述球磨中的球料比优选为10:1，球磨时间优选为6~8h。8 . The method for preparing layered magnetoelectric composite ceramics according to claim 5 , wherein in step (2), the drying temperature is 140-160° C., preferably 150° C., and the drying time is 140-160° C. 9 . The pre-sintering temperature is 400-500°C, and the pre-sintering time is 1.5-3h; the sintering temperature is 1210-1250°C, and the sintering time is 4-6h; the medium of the ball milling is preferably Dehydrated alcohol, the grinding balls are preferably Φ×3mm and Φ×7mm zirconia balls, and the mass ratio of the two is preferably 7~8:3~2; the ball-to-material ratio in the ball mill is preferably 10:1 , the ball milling time is preferably 6~8h. 9.根据权利要求5~8之一所述层状磁电复合陶瓷的制备方法，其特征在于，步骤（2）、（5）和（6）中，所述粘结剂为聚乙烯醇；所述压制成胚的压力为60~80Mpa；步骤（2）和（6）中，所述加热排胶的温度优选为500~650℃，加热排胶的时间优选为20~45min。9 . The method for preparing layered magnetoelectric composite ceramics according to claim 5 , wherein, in steps (2), (5) and (6), the binder is polyvinyl alcohol; 10 . The pressure of pressing into an embryo is 60-80 Mpa; in steps (2) and (6), the temperature of the heating and degumming is preferably 500-650° C., and the time of heating and degumming is preferably 20-45 min. 10.根据权利要求5~9之一所述层状磁电复合陶瓷的制备方法，其特征在于，步骤（3）中，所述压电相金属硝酸盐为五水合硝酸铋，硝酸钾，硝酸钠；所述压电相金属硝酸盐和钛酸正丁酯中铋：钠：钾：钛的摩尔比为1:1-x:x:2，x为0.18~0.2；所述搅拌的时间为3~5h，所述搅拌的转速为400~750 r/min；步骤（4）中，所述干燥的温度优选为105~135℃，所述干燥的时间优选为4.5~6h，所述预烧的温度优选400~500℃，预烧的时间优选1.5~3h，所述烧结温度优选为1120℃~1150℃，烧结时间优选为2~3h；步骤（5）中，所述烧结助剂优选为Bi2O3，所述烧结助剂用量优选为所述压电相粉体质量的2~3%；步骤（6）中，所述烧结的温度优选为1070~1120℃，烧结时间优选为2~3h。10. The method for preparing layered magnetoelectric composite ceramics according to any one of claims 5 to 9, wherein in step (3), the piezoelectric phase metal nitrate is bismuth nitrate pentahydrate, potassium nitrate, nitric acid Sodium; in the piezoelectric phase metal nitrate and n-butyl titanate, the molar ratio of bismuth: sodium: potassium: titanium is 1:1- x : x :2, and x is 0.18～0.2; the time of the stirring is 3~5h, the stirring speed is 400~750 r/min; in step (4), the drying temperature is preferably 105~135°C, the drying time is preferably 4.5~6h, and the pre-burning The temperature is preferably 400~500℃, the pre-sintering time is preferably 1.5~3h, the sintering temperature is preferably 1120℃~1150℃, and the sintering time is preferably 2~3h; in step (5), the sintering aid is preferably Bi 2 O 3 , the amount of the sintering aid is preferably 2-3% of the mass of the piezoelectric phase powder; in step (6), the sintering temperature is preferably 1070-1120° C., and the sintering time is preferably 2 ~3h.
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