CN106565233A - High-dielectric-constant and low-loss girdled hysteresis loop multiferroic composite ceramic and preparation method thereof - Google Patents
High-dielectric-constant and low-loss girdled hysteresis loop multiferroic composite ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000009768 microwave sintering Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 26
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 21
- 229910001626 barium chloride Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 13
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 13
- 230000008595 infiltration Effects 0.000 claims description 12
- 238000001764 infiltration Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 229910002113 barium titanate Inorganic materials 0.000 claims description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000009991 scouring Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000005498 polishing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 19
- 238000005245 sintering Methods 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 9
- 239000011858 nanopowder Substances 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 229910002771 BaFe12O19 Inorganic materials 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000007775 ferroic material Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000005294 ferromagnetic effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000009770 conventional sintering Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 230000005690 magnetoelectric effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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Abstract
The invention discloses a high-dielectric-constant and low-loss girdled hysteresis loop multiferroic composite ceramic and a preparation method thereof and belongs to the technical field of material preparation. The chemical composition expression of the composite ceramic is as follows: 0.88BaTiO3-0.12Ba(1-x)SrxFe12O19; and x is larger than or equal to 0.2 and is smaller than or equal to 0.8. 0.88BaTiO3-0.12BaFe12O19 is used as a matrix, the dielectric property of the ceramic is greatly improved through doping with Sr<2+>, the magnetism of the material is softened, and the material has the novel multiferroic performance. A feasible method is provided for practical application of the multiferroic composite ceramic. Besides, the microwave sintering method is different from general traditional sintering methods, the sintering time is very short, no temperature gradient exists in the sintering process, and the ceramic prepared by sintering nano powder prepared through combination of the method with the microwave hydrothermal method has the multiple advantages of being small in grain size, high in density and the like.
Description
Technical field
The invention belongs to technical field of material, is related to the preparation method of multi-ferroic material, and in particular to a kind of Gao Jie
Electric constant low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist and preparation method thereof.
Background technology
Also known as magnetoelectric material, it refers to and have simultaneously two or more basic iron multi-ferroic material（Ferroelectricity, iron
Magnetic and ferroelasticity）Material, the research of multi-ferroic material is inseparable, same material with the research of magnetoelectric effect
Middle magnetic and ferroelectricity coexist so that multi-ferroic material not only can make as single magnetic material and ferroelectric substance
With, meanwhile, magnetic causes material magnetization or additional magnetic field to cause thing with electric coupling effect, i.e. extra electric field in multi-ferroic material
Occurs electric polarization inside matter so that the material has in the application the higher free degree, is miniaturization and the multifunction of device
There is provided possible.
The general magnetoelectricity multiferroic composite ceramics being made up of dielectric phase and ferromagnetic phase two-phase has designability, controllable
Property, at room temperature there is higher magnetoelectric effect than single-phase multi-ferroic material.However, the performance of multiferroic composite ceramics takes
Certainly suitably constitute phase, the connectedness of two-phase, volume fraction, crystallite dimension and shape etc. factor in material.Because BaTiO3
It is typical ferroelectric phase, BaFe12O19It is typical ferromagnetic phase, so BaTiO3-BaFe12O19It is that most important multiferroic is combined
One of research system of ceramics（[1]Zijing Dong,et al.Fabrication,structure and properties
of BaTiO3–BaFe12O19composites with core–shell heterostructure[J].Journal of the
European Ceramic Society,2015,35:3513-3520）.Typically there is high resistivity to be magnetic electric compound material
Obtain the precondition of excellent magnetic electricity performance.BaTiO3-BaFe12O19BaFe in composite ceramics system12O19Resistivity ratio
BaTiO3Low several orders of magnitude, the movement that will necessarily there is electric charge after being combined in two-phase interface.Increase is led in the leakage for causing material, damages
Consumption increase, dielectric properties deteriorate.
The content of the invention
It is an object of the invention to provide a kind of high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist
And preparation method thereof, the method is simple to operate, reproducible, and composite ceramics dielectric constant obtained in Jing the method is high, and loss is little,
Ferroelectric hysteresis loop is in shape with a tight waist.
The present invention is to be achieved through the following technical solutions：
The invention discloses a kind of high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, the composite ceramic
The chemical composition of porcelain is expressed as：0.88BaTiO3-0.12Ba(1-x)SrxFe12O19, 0.2≤x≤0.8.
The invention also discloses a kind of preparation of high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist
Method, comprises the following steps：
1）Take TiCl4And BaCl2·2H2O, is successively dissolved in distilled water；
2）KOH is weighed, and is dissolved in step 1）In resulting solution, precursor liquid is obtained；
3）By precursor liquid at 180～220 DEG C, microwave hydrothermal reacts 25～35min, and product is obtained, and reaction is produced
Thing is washed to neutrality；
4）By Ba(1-x)SrxFe12O19, Ba in 0.2≤x≤0.82+, Sr2+, Fe3+Mol ratio, weigh Ba (NO3)2, Sr
(NO3)2With Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts solution ph to >=13, alkaline solution is obtained, by the alkalescence
At 170～190 DEG C, 25～30min of microwave hydrothermal is obtained product to solution, and product is washed to into neutrality；
5）By step 3）Obtained product and step 4）Obtained product is according to BaTiO3：Ba(1-x)
SrxFe12O19For 0.88：0.12 mixed in molar ratio post-drying, obtains mixed powder, then the PVA that volumetric concentration is 5% is added dropwise glues
Knot agent, until granulation is in unifonn spherical, is then pressed into type, and base substrate is obtained；
6）By base substrate in 600 DEG C of dumping 2h, ceramic green is obtained, it is then that ceramic green is micro- at 1000 DEG C～1100 DEG C
Ripple sinters 5min, and high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist is obtained.
Raw material TiCl used4、BaCl2·2H2The mol ratio of O and KOH is：TiCl4：BaCl2·2H2O：KOH=1：2：
10。
Step 6）After prepared high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, also include entering it
Row surface polishes, and by silver electrode, 10min is incubated at 600 DEG C, and the operation of burning infiltration silver electrode is obtained composite ceramics sample.
The temperature increasing schedule of burning infiltration silver electrode is：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with 3
DEG C/heating rate of min is warmed up to 500 DEG C from 200 DEG C, is finally warmed up to 600 DEG C from 500 DEG C with the programming rate of 5 DEG C/min,
During cooling, along with the furnace cooling.
Step 6）The temperature increasing schedule of the dumping is：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then
500 DEG C are warmed up to from 200 DEG C with the heating rate of 3 DEG C/min, finally 600 is warmed up to from 500 DEG C with the programming rate of 5 DEG C/min
DEG C, during cooling, along with the furnace cooling.
Step 6）The power output of the microwave sintering be 1500W, heating rate be 25 DEG C/min, and in 30min from
Room temperature to 1000 DEG C～1100 DEG C, during cooling, along with the furnace cooling.
Step 3）With step 4）Water scouring water is distilled water, is washed 5～6 times.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
More than 99.0%.
Compared with prior art, the present invention has following beneficial technique effect：
The preparation of high-k low-loss disclosed by the invention shape hysteresis curve multiferroic composite ceramics with a tight waist, by mixing
Miscellaneous Sr2+Ion, improves BaFe12O19Performance, so as on the premise of material ferromagnetic property is not affected, improve BaTiO3-
BaFe12O19The ferroelectric properties of composite ceramics so as to which multi-ferrum property further meets the requirement of practical application, advantage is notable, mainly
It is embodied in the following aspects：
1）Powder is prepared using microwave-hydrothermal method, size uniform little with crystal grain, degree of crystallinity is high, the reaction time is short etc. excellent
Point；
2）Using microwave sintering method sintering ceramics, different from general conventional sintering, sintering time is short, in sintering process not
There is thermograde, the method combines the ceramics of nano-powder sintering prepared by microwave-hydrothermal method and has crystallite dimension little, fine and close
Many advantages, such as spending high；
3）With TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2For raw material, raw material letter
It is single.
High-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist prepared by Jing the inventive method improves
Multiferroic BaTiO3-BaFe12O19Ferroelectric properties, size uniform little with crystal grain, degree of crystallinity is high, and dielectric constant is high, loss
It is little, it is multiferroic BaTiO the advantages of hysteresis curve coercivity is little3-BaFe12O19The practical application of composite ceramics provides one kind
Practicable method.
Description of the drawings
Fig. 1 is a kind of XRD spectrum of high-k low-loss shape hysteresis curve multiferroic composite ceramic material with a tight waist；
Fig. 2 is a kind of SEM photograph of high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist；Wherein,
（a）、（b）、（c）、（d）The composite ceramics of respectively x=0.2,0.4,0.6,0.8；
Fig. 3 is a kind of dielectric constant of high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist and loss
With the change collection of illustrative plates of frequency；
Fig. 4 is a kind of ferroelectric hysteresis loop of high-k low-loss shape hysteresis curve multiferroic composite ceramic material with a tight waist；
Fig. 5 is a kind of hysteresis curve of high-k low-loss shape hysteresis curve multiferroic composite ceramic material with a tight waist.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
Composite ceramics 0.88BaTiO in the present embodiment3-0.12Ba(1-x)SrxFe12O19Middle x=0.2, preparation method include with
Lower step：
1）By material molar ratio TiCl4：BaCl2·2H2O：KOH=1：2：10, first take TiCl4And BaCl2·2H2O, successively
In being dissolved in distilled water；
2）Then KOH is weighed, and is dissolved in step 1）In resulting solution, precursor liquid is obtained；
3）By step 2）At 180 DEG C, microwave hydrothermal reaction 35min is obtained product to obtained precursor liquid, will react
Product distillation washing 5～6 times, until neutral；
4）By Ba(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Mol ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O, in being dissolved in distilled water, adjusts solution ph to >=13, alkaline solution is obtained, by the alkaline solution 180
At DEG C, microwave hydrothermal 28min is obtained product, by product distillation washing 5～6 times, until neutral；
5）By step 3）With step 4）Obtained product is according to BaTiO3：Ba(1-x)SrxFe12O19For 0.88：0.12
Mixed in molar ratio post-drying, obtains mixed powder, adds the PVA binding agents that volumetric concentration is 5%, is then granulated（It is added dropwise
Volumetric concentration is 5% PVA binding agents until granulation is in spherical）, it is compressing, be obtained base substrate；
6）By base substrate in 600 DEG C of dumping 2h, ceramic green is obtained, it is then that ceramic green is micro- at 1000 DEG C～1100 DEG C
Ripple sinters 5min, and high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist is obtained.Wherein, the intensification system of dumping
Spend and be：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200 DEG C of intensifications
To 500 DEG C, finally 600 DEG C, during cooling are warmed up to from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling.The microwave burns
The power output of knot is 1500W, and heating rate is 25 DEG C/min, and from room temperature to 1000 DEG C～1100 DEG C in 30min,
During cooling, along with the furnace cooling；
Step 6）After prepared high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, then table is carried out to it
Mirror polish, by silver electrode, at 600 DEG C 10min is incubated, and burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule is：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200
DEG C 500 DEG C are warmed up to, are finally warmed up to 600 DEG C, during cooling from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
More than 99.0%.
Embodiment 2
Composite ceramics 0.88BaTiO in the present embodiment3-0.12Ba(1-x)SrxFe12O19Middle x=0.4, preparation method include with
Lower step：
1）By material molar ratio TiCl4：BaCl2·2H2O：KOH=1：2：10, first take TiCl4And BaCl2·2H2O, successively
In being dissolved in 40ml distilled water；
2）KOH is weighed, and is dissolved in step 1）In resulting solution, precursor liquid is obtained；
3）By step 2）At 200 DEG C, microwave hydrothermal reaction 30min is obtained product to obtained precursor liquid, will react
Product distillation washing 5～6 times, until neutral；
4）By Ba(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Mol ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O, in being dissolved in distilled water, adjusts solution ph to >=13, alkaline solution is obtained, by the alkaline solution 170
At DEG C, microwave hydrothermal 30min is obtained product, by product distillation washing 5～6 times, until neutral；
5）By step 3）With step 4）Obtained product is according to BaTiO3：Ba(1-x)SrxFe12O19For 0.88：0.12
Mixed in molar ratio post-drying, obtains mixed powder, adds the PVA binding agents that volumetric concentration is 5%, until granulation is in uniform ball
Shape, is then pressed into type, and base substrate is obtained；
6）By base substrate in 600 DEG C of dumping 2h, ceramic green is obtained, it is then that ceramic green is micro- at 1000 DEG C～1100 DEG C
Ripple sinters 5min, and high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist is obtained.Wherein, the intensification system of dumping
Spend and be：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200 DEG C of intensifications
To 500 DEG C, finally 600 DEG C, during cooling are warmed up to from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling；
The power output of microwave sintering be 1500W, heating rate be 25 DEG C/min, and in 30min from room temperature to
1000 DEG C～1100 DEG C, during cooling, along with the furnace cooling；
Step 6）After prepared high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, then table is carried out to it
Mirror polish, by silver electrode, at 600 DEG C 10min is incubated, and burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule is：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200
DEG C 500 DEG C are warmed up to, are finally warmed up to 600 DEG C, during cooling from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
More than 99.0%.
Embodiment 3
Composite ceramics 0.88BaTiO in this example3-0.12Ba(1-x)SrxFe12O19Middle x=0.6, preparation method includes following
Step：
1）By material molar ratio TiCl4：BaCl2·2H2O：KOH=1：2：10, first take TiCl4And BaCl2·2H2O, successively
In being dissolved in distilled water；
2）KOH is weighed, and is dissolved in step 1）In resulting solution, precursor liquid is obtained；
3）By step 2）At 220 DEG C, microwave hydrothermal reaction 25min is obtained product to obtained precursor liquid, will react
Product distillation washing 5～6 times, until neutral；
4）By Ba(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Mol ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O, in being dissolved in distilled water, adjusts solution ph to >=13, alkaline solution is obtained, by the alkaline solution 190
At DEG C, microwave hydrothermal 25min is obtained product, by product distillation washing 5～6 times, until neutral；
5）By step 3）With step 4）Obtained product is according to BaTiO3：Ba(1-x)SrxFe12O19For 0.88：0.12
Mixed in molar ratio post-drying, obtains mixed powder, adds the PVA binding agents that volumetric concentration is 5%, until granulation is in uniform ball
Shape, is then pressed into type, and base substrate is obtained；
6）By base substrate in 600 DEG C of dumping 2h, ceramic green is obtained, it is then that ceramic green is micro- at 1000 DEG C～1100 DEG C
Ripple sinters 5min, and high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist is obtained.Wherein, the intensification system of dumping
Spend and be：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200 DEG C of intensifications
To 500 DEG C, finally 600 DEG C, during cooling are warmed up to from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling.Microwave sintering
Power output is 1500W, and heating rate is 25 DEG C/min, and from room temperature to 1000 DEG C～1100 DEG C, cooling in 30min
When, along with the furnace cooling.
Step 6）After prepared high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, then table is carried out to it
Mirror polish, by silver electrode, at 600 DEG C 10min is incubated, and burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule is：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200
DEG C 500 DEG C are warmed up to, are finally warmed up to 600 DEG C, during cooling from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
More than 99.0%.
Embodiment 4
Composite ceramics 0.88BaTiO in this example3-0.12Ba(1-x)SrxFe12O19Middle x=0.8, preparation method includes following
Step：
1）By material molar ratio TiCl4：BaCl2·2H2O：KOH=1：2：10, first take TiCl4And BaCl2·2H2O, successively
In being dissolved in distilled water；
2）KOH is weighed, and is dissolved in step 1）In resulting solution, precursor liquid is obtained；
3）By step 2）At 190 DEG C, microwave hydrothermal reaction 28min is obtained product to obtained precursor liquid, will react
Product distillation washing 5～6 times, until neutral；
4）By Ba(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Mol ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O, in being dissolved in distilled water, adjusts solution ph to >=13, alkaline solution is obtained, by the alkaline solution 180
At DEG C, microwave hydrothermal 26min is obtained product, by product distillation washing 5～6 times, until neutral；
5）By step 3）With step 4）Obtained product is according to BaTiO3：Ba(1-x)SrxFe12O19For 0.88：0.12
Mixed in molar ratio post-drying, obtains mixed powder, adds the PVA binding agents that volumetric concentration is 5%, until granulation is in uniform ball
Shape, is then pressed into type, and base substrate is obtained；
6）By base substrate in 600 DEG C of dumping 2h, ceramic green is obtained, it is then that ceramic green is micro- at 1000 DEG C～1100 DEG C
Ripple sinters 5min, and high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist is obtained.Wherein, the intensification system of dumping
Spend and be：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200 DEG C of intensifications
To 500 DEG C, finally 600 DEG C, during cooling are warmed up to from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling.Microwave sintering
Power output is 1500W, and heating rate is 25 DEG C/min, and from room temperature to 1000 DEG C～1100 DEG C, cooling in 30min
When, along with the furnace cooling.
Step 6）After prepared high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, then table is carried out to it
Mirror polish, by silver electrode, at 600 DEG C 10min is incubated, and burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule is：With the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then with the heating rate of 3 DEG C/min from 200
DEG C 500 DEG C are warmed up to, are finally warmed up to 600 DEG C, during cooling from 500 DEG C with the programming rate of 5 DEG C/min, along with the furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
More than 99.0%.
Fig. 1 and Fig. 2 is referred to, implements the 0.88BaTiO prepared by above example3-0.12Ba(1-x)SrxFe12O19Composite ceramic
As can be seen that having synthesized BaTiO in above example in the XRD spectrum and SEM photograph of ceramic material3And Ba(1-x)
SrxFe12O19The composite ceramics for mutually coexisting.Simultaneously, it can be seen that without other dephasigns presence, and this two-phase degree of crystallinity is higher, does not have
There is interreaction, chemical compatibility is preferable.Referring to Fig. 3, it can be seen that dielectric constant reaches more than 10000, it is lost left 0.2
The right side, dielectric properties are excellent.Referring to Fig. 4, composite ceramics has more saturated ferroelectric hysteresis loop, and the iron of optimum is obtained in x=0.6
Electrically.Referring to Fig. 5, it can be seen that by the Sr that adulterates2+, the saturation magnetization of composite ceramics stills remain in higher level.And
And shape with a tight waist is presented, coercive field is less, makes the magnetic of material by " hard " change " soft ".
In sum, the present invention is prepared for 0.88BaTiO by microwave-hydrothermal method and microwave sintering method3-0.12Ba(1-x)
SrxFe12O19Composite ceramics.With 0.88BaTiO3-0.12Ba(1-x)SrxFe12O19Based on, by the Sr that adulterates2+Greatly improve
Its dielectric properties, by the magnetic softening of material, is presented a kind of new multi-ferrum property.And microwave sintering method is different from general
Conventional sintering, sintering time is very short, there is no thermograde in sintering process, and the method combines nanometer prepared by microwave-hydrothermal method
The ceramics of powder sintering have many advantages, such as crystallite dimension is little, and consistency is high, are that the practical application of Multiferroic composite material is carried
A kind of practicable method is supplied.
Employing 0.88BaTiO disclosed by the invention3-0.12Ba(1-x)SrxFe12O19Composite ceramics and preparation method thereof has can
Can become and prepare Multiferroic composite material technically and financially and excellent new formula.
Claims (9)
1. a kind of high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, it is characterised in that the composite ceramics
Chemical composition be expressed as：0.88BaTiO3-0.12Ba(1-x)SrxFe12O19, 0.2≤x≤0.8.
2. the preparation method of a kind of high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist, it is characterised in that
Comprise the following steps：
1) TiCl is taken4And BaCl2·2H2O, is successively dissolved in distilled water；
2) KOH is weighed, and is dissolved in step 1) in resulting solution, precursor liquid is obtained；
3) by precursor liquid at 180～220 DEG C, microwave hydrothermal reacts 25～35min, product is obtained, by reaction product water
It is washed till neutrality；
4) by Ba(1-x)SrxFe12O19, Ba in 0.2≤x≤0.82+, Sr2+, Fe3+Mol ratio, weigh Ba (NO3)2, Sr (NO3)2
With Fe (NO3)3·9H2O, in being dissolved in distilled water, adjusts solution ph to >=13, and alkaline solution is obtained, and the alkaline solution is existed
At 170～190 DEG C, 25～30min of microwave hydrothermal is obtained product, and product is washed to into neutrality；
5) by step 3) obtained in product and step 4) obtained in product according to BaTiO3：Ba(1-x)SrxFe12O19For
0.88：0.12 mixed in molar ratio post-drying, obtains mixed powder, then the PVA binding agents that volumetric concentration is 5% are added dropwise, until
Granulation is in unifonn spherical, is then pressed into type, and base substrate is obtained；
6) by base substrate in 600 DEG C of dumping 2h, ceramic green is obtained, then microwave burns at 1000 DEG C～1100 DEG C by ceramic green
Knot 5min, is obtained high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist.
3. the system of a kind of high-k low-loss according to claim 2 shape hysteresis curve multiferroic composite ceramics with a tight waist
Preparation Method, it is characterised in that raw material TiCl used4、BaCl2·2H2The mol ratio of O and KOH is：TiCl4：BaCl2·2H2O：
KOH=1：2：10.
4. the system of a kind of high-k low-loss according to claim 2 shape hysteresis curve multiferroic composite ceramics with a tight waist
Preparation Method, it is characterised in that step 6) high-k low-loss shape hysteresis curve multiferroic composite ceramics with a tight waist is obtained after, also
Surface polishing is carried out including to it, by silver electrode, 10min is incubated at 600 DEG C, the operation of burning infiltration silver electrode is obtained composite ceramics
Sample.
5. the system of a kind of high-k low-loss according to claim 4 shape hysteresis curve multiferroic composite ceramics with a tight waist
Preparation Method, it is characterised in that the temperature increasing schedule of burning infiltration silver electrode is：With the heating rate of 2 DEG C/min from room temperature to 200
DEG C, then 500 DEG C are warmed up to from 200 DEG C with the heating rate of 3 DEG C/min, finally risen from 500 DEG C with the programming rate of 5 DEG C/min
Temperature is to 600 DEG C, during cooling, along with the furnace cooling.
6. the system of a kind of high-k low-loss according to claim 2 shape hysteresis curve multiferroic composite ceramics with a tight waist
Preparation Method, it is characterised in that step 6) temperature increasing schedule of the dumping is：With the heating rate of 2 DEG C/min from room temperature to
200 DEG C, then 500 DEG C are warmed up to from 200 DEG C with the heating rate of 3 DEG C/min, finally with the programming rate of 5 DEG C/min from 500
DEG C 600 DEG C, during cooling are warmed up to, along with the furnace cooling.
7. the system of a kind of high-k low-loss according to claim 2 shape hysteresis curve multiferroic composite ceramics with a tight waist
Preparation Method, it is characterised in that step 6) microwave sintering power output be 1500W, heating rate be 25 DEG C/min, and
From room temperature to 1000 DEG C～1100 DEG C in 30min, during cooling, along with the furnace cooling.
8. the system of a kind of high-k low-loss according to claim 2 shape hysteresis curve multiferroic composite ceramics with a tight waist
Preparation Method, it is characterised in that step 3) and step 4) water scouring water be distilled water, wash 5～6 times.
9. the system of a kind of high-k low-loss according to claim 2 shape hysteresis curve multiferroic composite ceramics with a tight waist
Preparation Method, it is characterised in that raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2's
Purity is more than 99.0%.
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| CN103787420A (en) * | 2014-01-25 | 2014-05-14 | 陕西科技大学 | Method for preparing SrFe12O19 magnetic nano powder by using microwave hydrothermal method |
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| CN109678495A (en) * | 2019-01-15 | 2019-04-26 | 陕西科技大学 | A kind of BaTiO3-Sr2CoMoO6Magnetoelectric ceramic and preparation method thereof |
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