CN106565233B - A kind of high dielectric constant low-loss is girdled the waist shape hysteresis loop multiferroic composite ceramics and preparation method thereof - Google Patents
A kind of high dielectric constant low-loss is girdled the waist shape hysteresis loop multiferroic composite ceramics and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000009768 microwave sintering Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 46
- 238000001816 cooling Methods 0.000 claims description 36
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 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
- 238000010792 warming Methods 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
- 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
- 229910003074 TiCl4 Inorganic materials 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
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 229910002113 barium titanate Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 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
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000009991 scouring Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 18
- 238000005245 sintering Methods 0.000 abstract description 10
- 230000005291 magnetic effect Effects 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 238000009770 conventional sintering Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000011858 nanopowder Substances 0.000 abstract description 2
- 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
- 230000007935 neutral effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000007775 ferroic material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005294 ferromagnetic effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 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
- 238000000748 compression moulding Methods 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
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process 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
- C04B35/01—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
- 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 kind of high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist and preparation method thereof, belong to technical field of material.The chemical composition of the composite ceramics is expressed are as follows: 0.88BaTiO3‑0.12Ba(1‑x)SrxFe12O19, 0.2≤x≤0.8.The present invention is with 0.88BaTiO3‑0.12BaFe12O19For matrix, pass through doping Sr2+Its dielectric properties is greatly improved, by the magnetic softening of material, a kind of novel multi-ferrum property is presented.A kind of practicable method is provided for the practical application of multiferroic composite ceramics.And many advantages, such as microwave sintering method is different from general conventional sintering, and sintering time is very short, and temperature gradient is not present in sintering process, and the ceramics of the nano-powder sintering of the method combination microwave-hydrothermal method preparation have crystallite dimension small, and consistency is high.
Description
Technical field
The invention belongs to technical field of material, are related to the preparation method of multi-ferroic material, and in particular to a kind of Gao Jie
Electric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist and preparation method thereof.
Background technique
Multi-ferroic material is also known as magnetoelectric material, it refers to while having two or more basic iron (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 coexists so that multi-ferroic material can be used as single magnetic material and ferroelectric substance not only to make
With, meanwhile, the coupling effect of magnetic and electricity in multi-ferroic material, i.e. extra electric field cause substance magnetization or additional magnetic field to lead to object
Occur electric polarization inside matter, so that the material has higher freedom degree in the application, it is the miniaturization and multifunction of device
Provide possibility.
The magnetoelectricity multiferroic composite ceramics being generally made of dielectric phase and ferromagnetic phase two-phase have designability, controllable
Property, have many advantages, such as stronger magnetoelectric effect than single-phase multi-ferroic material at room temperature.However, the performance of multiferroic composite ceramics takes
Certainly phase, the connectivity of two-phase, volume fraction, crystallite dimension and shape etc. factor are suitably formed in material.Because of BaTiO3
It is typical ferroelectric phase, BaFe12O19It is typical ferromagnetic phase, so BaTiO3-BaFe12O19It is that most important multiferroic is compound
One of the 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).Generally having high resistivity is magnetic electric compound material
Obtain the precondition of excellent magnetic electricity performance.BaTiO3-BaFe12O19BaFe in composite ceramics system12O19Resistivity ratio
BaTiO3Low several orders of magnitude in two-phase interface will necessarily have the movement of charge after compound.Cause the leakage of material to lead increase, damages
Consumption increases, and dielectric properties deteriorate.
Summary of the invention
The purpose of the present invention is to provide a kind of high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist
And preparation method thereof, this method is easy to operate, and reproducible, through the height of composite ceramics dielectric constant made from this method, loss is small,
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 dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist, the composite ceramics
The chemical composition of porcelain is expressed are as follows: 0.88BaTiO3-0.12Ba(1-x)SrxFe12O19, 0.2≤x≤0.8.
The invention also discloses a kind of preparations of high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist
Method, comprising 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) acquired solution, precursor liquid is made；
3) by precursor liquid at 180~220 DEG C, microwave hydrothermal reacts 25~35min, and reaction product is made, and reaction is produced
Object is washed to neutrality；
4) Ba is pressed(1-x)SrxFe12O19, Ba in 0.2≤x≤0.82+, Sr2+, Fe3+Molar ratio, weigh Ba (NO3)2, Sr
(NO3)2With Fe (NO3)3·9H2O is dissolved in distilled water, is adjusted solution ph to >=13, alkaline solution is made, by the alkalinity
Solution is at 170~190 DEG C, 25~30min of microwave hydrothermal, and reaction product is made, reaction product is washed to neutrality；
5) by reaction product made from reaction product made from step 3) and step 4) according to BaTiO3: Ba(1-x)
SrxFe12O19To dry after the molar ratio mixing of 0.88:0.12, mixed powder is obtained, then the PVA that volumetric concentration is 5% is added dropwise and glues
Agent is tied, until being granulated is in unifonn spherical, is then pressed into type, green body is made；
6) green body is obtained into ceramic green in 600 DEG C of dumping 2h, it is then that ceramic green is micro- at 1000 DEG C~1100 DEG C
Wave is sintered 5min, and high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made.
Raw material TiCl used4、BaCl2·2H2The molar ratio of O and KOH are as follows: TiCl4: BaCl2·2H2O:KOH=1:2:
10。
Step 6) be made high dielectric constant low-loss girdle the waist shape hysteresis loop multiferroic composite ceramics after, further include to its into
Row surface polishing, by silver electrode, in 600 DEG C of heat preservation 10min, composite ceramics sample is made in the operation of burning infiltration silver electrode.
The temperature increasing schedule of burning infiltration silver electrode are as follows: 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 warming up to 500 DEG C from 200 DEG C, 600 DEG C finally are warming up to from 500 DEG C with the heating rate of 5 DEG C/min,
When cooling, furnace cooling.
The temperature increasing schedule of dumping described in step 6) are as follows: with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then
500 DEG C are warming up to from 200 DEG C with the heating rate of 3 DEG C/min, is finally warming up to 600 from 500 DEG C with the heating rate of 5 DEG C/min
DEG C, when cooling, furnace cooling.
The output power of microwave sintering described in step 6) be 1500W, heating rate be 25 DEG C/min, and in 30min from
Room temperature is to 1000 DEG C~1100 DEG C, when cooling, furnace cooling.
Step 3) and step 4) water scouring water are distilled water, are washed 5~6 times.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
99.0% or more.
Compared with prior art, the invention has the following beneficial technical effects:
The preparation of high dielectric constant low-loss disclosed by the invention shape hysteresis loop multiferroic composite ceramics with a tight waist, by mixing
Miscellaneous Sr2+Ion improves BaFe12O19Performance improve BaTiO thus under the premise of not influencing material ferromagnetic property3-
BaFe12O19The ferroelectric properties of composite ceramics makes its multi-ferrum property further meet the requirement of practical application, and advantage is significant, mainly
It is embodied in the following aspects:
1) powder is prepared using microwave-hydrothermal method, has crystal grain small, of uniform size, crystallinity is high, and the reaction time is short etc. excellent
Point；
2) using microwave sintering method sintering ceramics, it is different from general conventional sintering, sintering time is short, in sintering process not
There are temperature gradient, the ceramics of the nano-powder sintering of the method combination microwave-hydrothermal method preparation have crystallite dimension small, fine and close
Spend many advantages, such as 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 dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist through the method for the present invention preparation improve
Multiferroic BaTiO3-BaFe12O19Ferroelectric properties, have crystal grain small, of uniform size, crystallinity is high, and dielectric constant is high, loss
Small, the advantages that hysteresis loop coercivity is small is multiferroic BaTiO3-BaFe12O19The practical application of composite ceramics provides one kind
Practicable method.
Detailed description of the invention
Fig. 1 is a kind of XRD spectrum of high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramic material with a tight waist；
Fig. 2 is a kind of SEM photograph of high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist；Wherein,
(a) and (b), (c), (d) are respectively the composite ceramics of x=0.2,0.4,0.6,0.8；
Fig. 3 be a kind of high dielectric constant low-loss girdle the waist shape hysteresis loop multiferroic composite ceramics dielectric constant and loss
With the variation map of frequency；
Fig. 4 is a kind of ferroelectric hysteresis loop of high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramic material with a tight waist；
Fig. 5 is a kind of hysteresis loop of high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramic material with a tight waist.
Specific embodiment
Below 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) material molar ratio TiCl is pressed4: BaCl2·2H2O:KOH=1:2:10 first takes TiCl4And BaCl2·2H2O, successively
It is dissolved in distilled water；
2) KOH then is weighed, and be dissolved in step 1) acquired solution, precursor liquid is made；
3) by precursor liquid made from step 2 at 180 DEG C, microwave hydrothermal reacts 35min, and reaction product is made, will react
Product distillation washing 5~6 times, until neutral；
4) Ba is pressed(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Molar ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O is dissolved in distilled water, is adjusted solution ph to >=13, alkaline solution is made, by the alkaline solution 180
At DEG C, reaction product is made in microwave hydrothermal 28min, by reaction product distillation washing 5~6 times, until neutral；
5) by reaction product made from step 3) and step 4) according to BaTiO3: Ba(1-x)SrxFe12O19For 0.88:0.12's
It is dried after molar ratio mixing, obtains mixed powder, added the PVA binder that volumetric concentration is 5%, be then granulated and (be added dropwise
The PVA binder that volumetric concentration is 5% is until be granulated in spherical), compression moulding, green body is made；
6) green body is obtained into ceramic green in 600 DEG C of dumping 2h, it is then that ceramic green is micro- at 1000 DEG C~1100 DEG C
Wave is sintered 5min, and high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made.Wherein, the heating system of dumping
Degree are as follows: with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then heated up with the heating rate of 3 DEG C/min from 200 DEG C
To 500 DEG C, 600 DEG C are finally warming up to from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling.The microwave is burnt
The output power 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,
When cooling, furnace cooling；
After high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made in step 6), then table is carried out to it
Face polishing, by silver electrode, in 600 DEG C of heat preservation 10min, burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule are as follows: 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 warming up to, are finally warming up to 600 DEG C from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
99.0% or more.
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) material molar ratio TiCl is pressed4: BaCl2·2H2O:KOH=1:2:10 first takes TiCl4And BaCl2·2H2O, successively
It is dissolved in 40ml distilled water；
2) KOH is weighed, and is dissolved in step 1) acquired solution, precursor liquid is made；
3) by precursor liquid made from step 2 at 200 DEG C, microwave hydrothermal reacts 30min, and reaction product is made, will react
Product distillation washing 5~6 times, until neutral；
4) Ba is pressed(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Molar ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O is dissolved in distilled water, is adjusted solution ph to >=13, alkaline solution is made, by the alkaline solution 170
At DEG C, reaction product is made in microwave hydrothermal 30min, by reaction product distillation washing 5~6 times, until neutral；
5) by reaction product made from step 3) and step 4) according to BaTiO3: Ba(1-x)SrxFe12O19For 0.88:0.12's
It is dried after molar ratio mixing, obtains mixed powder, add the PVA binder that volumetric concentration is 5%, until being granulated is in uniform ball
Shape is then pressed into type, and green body is made；
6) green body is obtained into ceramic green in 600 DEG C of dumping 2h, it is then that ceramic green is micro- at 1000 DEG C~1100 DEG C
Wave is sintered 5min, and high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made.Wherein, the heating system of dumping
Degree are as follows: with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then heated up with the heating rate of 3 DEG C/min from 200 DEG C
To 500 DEG C, 600 DEG C are finally warming up to from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling；
The output power 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, when cooling, furnace cooling；
After high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made in step 6), then table is carried out to it
Face polishing, by silver electrode, in 600 DEG C of heat preservation 10min, burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule are as follows: 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 warming up to, are finally warming up to 600 DEG C from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
99.0% or more.
Embodiment 3
Composite ceramics 0.88BaTiO in this example3-0.12Ba(1-x)SrxFe12O19Middle x=0.6, preparation method include following
Step:
1) material molar ratio TiCl is pressed4: BaCl2·2H2O:KOH=1:2:10 first takes TiCl4And BaCl2·2H2O, successively
It is dissolved in distilled water；
2) KOH is weighed, and is dissolved in step 1) acquired solution, precursor liquid is made；
3) by precursor liquid made from step 2 at 220 DEG C, microwave hydrothermal reacts 25min, and reaction product is made, will react
Product distillation washing 5~6 times, until neutral；
4) Ba is pressed(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Molar ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O is dissolved in distilled water, is adjusted solution ph to >=13, alkaline solution is made, by the alkaline solution 190
At DEG C, reaction product is made in microwave hydrothermal 25min, by reaction product distillation washing 5~6 times, until neutral；
5) by reaction product made from step 3) and step 4) according to BaTiO3: Ba(1-x)SrxFe12O19For 0.88:0.12's
It is dried after molar ratio mixing, obtains mixed powder, add the PVA binder that volumetric concentration is 5%, until being granulated is in uniform ball
Shape is then pressed into type, and green body is made；
6) green body is obtained into ceramic green in 600 DEG C of dumping 2h, it is then that ceramic green is micro- at 1000 DEG C~1100 DEG C
Wave is sintered 5min, and high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made.Wherein, the heating system of dumping
Degree are as follows: with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then heated up with the heating rate of 3 DEG C/min from 200 DEG C
To 500 DEG C, 600 DEG C are finally warming up to from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling.Microwave sintering
Output power is 1500W, and heating rate is 25 DEG C/min, and from room temperature to 1000 DEG C~1100 DEG C in 30min, cooling
When, furnace cooling.
After high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made in step 6), then table is carried out to it
Face polishing, by silver electrode, in 600 DEG C of heat preservation 10min, burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule are as follows: 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 warming up to, are finally warming up to 600 DEG C from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
99.0% or more.
Embodiment 4
Composite ceramics 0.88BaTiO in this example3-0.12Ba(1-x)SrxFe12O19Middle x=0.8, preparation method include following
Step:
1) material molar ratio TiCl is pressed4: BaCl2·2H2O:KOH=1:2:10 first takes TiCl4And BaCl2·2H2O, successively
It is dissolved in distilled water；
2) KOH is weighed, and is dissolved in step 1) acquired solution, precursor liquid is made；
3) by precursor liquid made from step 2 at 190 DEG C, microwave hydrothermal reacts 28min, and reaction product is made, will react
Product distillation washing 5~6 times, until neutral；
4) Ba is pressed(1-x)SrxFe12O19Middle Ba2+, Sr2+, Fe3+Molar ratio, weigh Ba (NO3)2, Sr (NO3)2And Fe
(NO3)3·9H2O is dissolved in distilled water, is adjusted solution ph to >=13, alkaline solution is made, by the alkaline solution 180
At DEG C, reaction product is made in microwave hydrothermal 26min, by reaction product distillation washing 5~6 times, until neutral；
5) by reaction product made from step 3) and step 4) according to BaTiO3: Ba(1-x)SrxFe12O19For 0.88:0.12's
It is dried after molar ratio mixing, obtains mixed powder, add the PVA binder that volumetric concentration is 5%, until being granulated is in uniform ball
Shape is then pressed into type, and green body is made；
6) green body is obtained into ceramic green in 600 DEG C of dumping 2h, it is then that ceramic green is micro- at 1000 DEG C~1100 DEG C
Wave is sintered 5min, and high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made.Wherein, the heating system of dumping
Degree are as follows: with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, then heated up with the heating rate of 3 DEG C/min from 200 DEG C
To 500 DEG C, 600 DEG C are finally warming up to from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling.Microwave sintering
Output power is 1500W, and heating rate is 25 DEG C/min, and from room temperature to 1000 DEG C~1100 DEG C in 30min, cooling
When, furnace cooling.
After high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made in step 6), then table is carried out to it
Face polishing, by silver electrode, in 600 DEG C of heat preservation 10min, burning infiltration silver electrode obtains composite ceramics sample.Burning infiltration silver electrode
Temperature increasing schedule are as follows: 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 warming up to, are finally warming up to 600 DEG C from 500 DEG C with the heating rate of 5 DEG C/min, when cooling, furnace cooling.
Raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2Purity be
99.0% or more.
Referring to Figure 1 and Fig. 2, implement 0.88BaTiO prepared by above example3-0.12Ba(1-x)SrxFe12O19Composite ceramic
As can be seen that having synthesized BaTiO in above embodiments in the XRD spectrum and SEM photograph of ceramic material3And Ba(1-x)
SrxFe12O19The composite ceramics mutually coexisted.Simultaneously, it can be seen that exist without other miscellaneous phases, and this two-phase 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 10000 or more, and loss is on 0.2 left side
The right side, dielectric properties are excellent.Referring to fig. 4, composite ceramics have more saturated ferroelectric hysteresis loop, obtain optimal iron in x=0.6
Electrically.Referring to Fig. 5, it can be seen that by adulterating Sr2+, the saturation magnetization of composite ceramics stills remain in higher level.And
And shape with a tight waist is presented, coercive field is smaller, makes the magnetism of material by " hard " change " soft ".
In conclusion 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)SrxFe12O19For matrix, pass through doping Sr2+Greatly improve
A kind of novel multi-ferrum property is presented in the magnetic softening of material by its dielectric properties.And microwave sintering method is different from general
Conventional sintering, sintering time is very short, and temperature gradient, the nanometer of the method combination microwave-hydrothermal method preparation are not present in sintering process
Many advantages, such as ceramics of powder sintering have crystallite dimension small, and consistency is high mentions for the practical application of Multiferroic composite material
A kind of practicable method is supplied.
It is disclosed by the invention to use 0.88BaTiO3-0.12Ba(1-x)SrxFe12O19Composite ceramics and preparation method thereof have can
Preparation Multiferroic composite material technically and financially simultaneous excellent new formula can be become.
Claims (9)
- A kind of shape hysteresis loop multiferroic composite ceramics 1. high dielectric constant low-loss is girdled the waist, which is characterized in that the composite ceramics Chemical composition expression are as follows: 0.88BaTiO3-0.12Ba(1-x)SrxFe12O19, 0.2≤x≤0.8.
- The preparation method of shape hysteresis loop multiferroic composite ceramics 2. a kind of high dielectric constant low-loss is girdled the waist, which is characterized in that The following steps are included:1) TiCl is taken4And BaCl2·2H2O is successively dissolved in distilled water；2) KOH is weighed, and is dissolved in step 1) acquired solution, precursor liquid is made；3) by precursor liquid at 180~220 DEG C, microwave hydrothermal reacts 25~35min, reaction product is made, by reaction product water It is washed till neutrality；4) Ba is pressed(1-x)SrxFe12O19, Ba in 0.2≤x≤0.82+, Sr2+, Fe3+Molar ratio, weigh Ba (NO3)2, Sr (NO3)2 With Fe (NO3)3·9H2O is dissolved in distilled water, adjusts solution ph to >=13, alkaline solution is made, which is existed At 170~190 DEG C, 25~30min of microwave hydrothermal is made reaction product, reaction product is washed to neutrality；5) by reaction product made from reaction product made from step 3) and step 4) according to BaTiO3: Ba(1-x)SrxFe12O19For It is dried after the molar ratio mixing of 0.88:0.12, obtains mixed powder, then the PVA binder that volumetric concentration is 5% is added dropwise, until Being granulated is in unifonn spherical, is then pressed into type, and green body is made；6) green body is obtained into ceramic green in 600 DEG C of dumping 2h, then microwave is burnt at 1000 DEG C~1100 DEG C by ceramic green 5min is tied, high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made.
- The system of shape hysteresis loop multiferroic composite ceramics 3. a kind of high dielectric constant low-loss according to claim 2 is girdled the waist Preparation Method, which is characterized in that raw material TiCl used4、BaCl2·2H2The molar ratio of O and KOH are as follows: TiCl4: BaCl2·2H2O: KOH=1:2:10.
- The system of shape hysteresis loop multiferroic composite ceramics 4. a kind of high dielectric constant low-loss according to claim 2 is girdled the waist Preparation Method, which is characterized in that after high dielectric constant low-loss shape hysteresis loop multiferroic composite ceramics with a tight waist are made in step 6), also Including carrying out surface polishing to it, by silver electrode, in 600 DEG C of heat preservation 10min, composite ceramics are made in the operation of burning infiltration silver electrode Sample.
- The system of shape hysteresis loop multiferroic composite ceramics 5. a kind of high dielectric constant low-loss according to claim 4 is girdled the waist Preparation Method, which is characterized in that the temperature increasing schedule of burning infiltration silver electrode are as follows: with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, 500 DEG C then are warming up to from 200 DEG C with the heating rate of 3 DEG C/min, is finally risen with the heating rate of 5 DEG C/min from 500 DEG C Temperature is to 600 DEG C, when cooling, furnace cooling.
- The system of shape hysteresis loop multiferroic composite ceramics 6. a kind of high dielectric constant low-loss according to claim 2 is girdled the waist Preparation Method, which is characterized in that the temperature increasing schedule of the step 6) dumping are as follows: with the heating rate of 2 DEG C/min from room temperature to 200 DEG C, 500 DEG C then are warming up to from 200 DEG C with the heating rate of 3 DEG C/min, finally with the heating rate of 5 DEG C/min from 500 DEG C it is warming up to 600 DEG C, when cooling, furnace cooling.
- The system of shape hysteresis loop multiferroic composite ceramics 7. a kind of high dielectric constant low-loss according to claim 2 is girdled the waist Preparation Method, which is characterized in that the output power of the step 6) microwave sintering is 1500W, and heating rate is 25 DEG C/min, and From room temperature to 1000 DEG C~1100 DEG C in 30min, when cooling, furnace cooling.
- The system of shape hysteresis loop multiferroic composite ceramics 8. a kind of high dielectric constant low-loss according to claim 2 is girdled the waist Preparation Method, which is characterized in that step 3) and step 4) water scouring water are distilled water, are washed 5~6 times.
- The system of shape hysteresis loop multiferroic composite ceramics 9. a kind of high dielectric constant low-loss according to claim 2 is girdled the waist Preparation Method, which is characterized in that raw material TiCl4、BaCl2·2H2O、Fe(NO3)3·9H2O、KOH、Sr(NO3)2With Ba (NO3)2's Purity is 99.0% or more.
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| CN103979956A (en) * | 2014-05-30 | 2014-08-13 | 陕西科技大学 | Method for preparing binderless BaTiO3 ceramic through microwave-assisted method |
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| CN103979956A (en) * | 2014-05-30 | 2014-08-13 | 陕西科技大学 | Method for preparing binderless BaTiO3 ceramic through microwave-assisted method |
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| Development of Novel Multiferroic Composites Based on BaTiO3 and Hexagonal Ferrites;D.V.Karpinsky et al.;《Materials Research Society》;20091231;第1161卷;第1-6页 |
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