CN105777111B - A kind of dielectric ceramic material and preparation method thereof of huge dielectric constant low-dielectric loss - Google Patents
A kind of dielectric ceramic material and preparation method thereof of huge dielectric constant low-dielectric loss Download PDFInfo
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Abstract
The invention discloses a kind of dielectric ceramic materials of huge dielectric constant low-dielectric loss, it carries out the SrTiO with giant dielectric performance of Sr substitutions for two kinds of elements of Sm and Ba jointly3Base ceramic material, chemical formula BaxSr0.97‑xSm0.02TiO3, the molar fraction of wherein x expressions Ba, 0.1≤x≤0.4；The molar fraction of Sm is fixed as 0.02.The present invention is with SrCO3、Sm2O3、TiO2、BaCO3For raw material, and press BaxSr0.97‑xSm0.02TiO3Stoichiometric ratio mixed after ball milling, drying, pre-burning, secondary ball milling, granulation, molding, sintering and etc. prepare the dielectric ceramic material, the dielectric constants of resulting materials it is high (>20000), dielectric loss it is low (<0.05), there is excellent temperature and frequency stability；And the preparation method being related to is simple, reproducible, high yield rate, and it is at low cost, it is suitble to promote and apply.
Description
Technical field
The invention belongs to information functional material fields, and in particular to a kind of huge dielectric constant with broad temperature, broadband stability
Dielectric ceramic material of low-dielectric loss and preparation method thereof.
Background technology
Microelectronics information technology it is fast-developing to being miniaturized of electronic component, it is integrated that more stringent requirements are proposed,
As the important component part of electronic component, the research of dielectric ceramics is more and more paid close attention to by people.With information
The technical field especially need of work of the development of electronics and microelectronic industry and extreme environment, have good temperature and
The huge dielectric constant of frequency stability, the dielectric substance of low-dielectric loss have a wide range of applications.
In recent years, the dielectric substance with huge dielectric constant is received more and more attention in new material circle, these tools
There is the dielectric substance of huge dielectric constant to be concentrated mainly on CaCu3Ti4O12Ceramics and its modified material, Fe base composite perofskite materials
Material, metal co-doped NiO ceramic materials and BaTi1-x(Ni1/2W1/2)xO3Ceramic material etc..These are with huge dielectric constant
Dielectric substance is often related with internal interfacial polarization, relaxation dipole etc., and often have high dielectric loss (>
0.1), it is difficult to be widely used in the electronic component that capacitor, memory etc. need high dielectric constant and low dielectric loss.Institute
With, prepare it is a kind of not only there is high dielectric constant, but also there is low dielectric loss, while taking into account good temperature and frequency stabilization
Property dielectric substance have apparent practical significance.
SrTiO3For typical quantum paraelectrics ceramic material, there is no the curie points generated by spontaneous polarization, have
Low dielectric loss and excellent Jie's temperature stability, in dielectric ceramic field by years of researches.Changed by rear-earth-doped
Property and protective atmosphere sintering, its extensive use in giant dielectric Material Field can be widened.There is article to show rear-earth-doped amount about
When being 0.01~0.03, SrTiO can be significantly improved3The dielectric constant of base ceramics, but since the effect of defect ion can produce
Raw relaxation phenomena, larger dielectric loss relaxation peak limits it and applies in a high temperauture environment；Protective atmosphere sintering
SrTiO3Ceramics due to the interfacial polarization of crystal particle crystal boundary, often generate larger dielectric loss (>0.1).How low Jie is being maintained
On the basis of electrical loss, the SrTiO with huge dielectric constant and broad temperature, broadband stability is obtained3Ceramics are a current big skills
Art research hotspot.
Invention content
The object of the present invention is to provide a kind of dielectric ceramic material of huge dielectric constant low-dielectric loss, the dielectric materials
Constant is high, dielectric loss is low, and has excellent temperature and frequency stability；And the preparation method being related to is simple, it is reproducible,
High yield rate, it is at low cost, it is suitble to promote and apply.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of dielectric ceramic material of huge dielectric constant low-dielectric loss, it takes to carry out Sr jointly using Ba and Sm
The SrTiO in generation3Base giant dielectric ceramic material, general formula BaxSr0.97-xSm0.02TiO3, the wherein value range of x is 0.1≤x
The doping of≤0.4, Sm are fixed as 0.02.
A kind of preparation method of the dielectric ceramic material of above-mentioned huge dielectric constant low-dielectric loss, includes the following steps：
1) with SrCO3、Sm2O3、TiO2And BaCO3For raw material, by BaxSr0.97-xSm0.02TiO3Stoichiometric ratio claimed
Gained mixed raw material is carried out ball milling, drying by amount, mixing；
2) drying product progress pre-burning, secondary ball milling obtained by step 1) are obtained into pre-burning powder, then adds binder granulation
And it is sieved, compression moulding, obtains ceramic body after dumping；
3) gained ceramic body is placed under protective atmosphere and is sintered, it is cooling that the low dielectric damage of the huge dielectric constant is made
The dielectric ceramic material of consumption.
In said program, secondary ball milling process described in the step 1) mechanical milling process and step 2) uses roller rotating vane type
Ball milling；For the ball-milling medium used for zirconia ball and absolute ethyl alcohol, rotational speed of ball-mill is 800~1000r/min, Ball-milling Time 18
~30 hours.
In said program, the calcined temperature is 1100~1180 DEG C, and pre-burning soaking time is 2~4h.
In said program, sintering process described in step 3) is：It is heated to 900~1000 with the rate of 4~8 DEG C/min
DEG C, 1400~1550 DEG C of 2~4h of heat preservation sintering are then warming up to the rate of 2~5 DEG C/min, then with the rate of 2~5 DEG C/min
900~1100 DEG C are cooled to, finally with stove natural cooling.
In said program, the drying temperature is 100~120 DEG C, and drying time is 18~30 hours.
In said program, the binder is polyvinyl alcohol water solution, and mass concentration is 2.5~5wt%.
In said program, the mass ratio of the binder volume and pre-burning powder is 0.04~0.08ml:g.
In said program, the pressure that the compression moulding process uses is molded for 10~15Mpa using uniaxial Self-pressurizing agri
Device, a diameter of 12mm, the thickness of gained ceramic body are 0.7~1.2mm.
In said program, the circulating rate of protective atmosphere is 50~100mL/min in the sintering process, and protective atmosphere is
Nitrogen or argon gas.
In said program, before carrying out the step 3) sintering process, sintering furnace interior conduit is carried out being evacuated to body in advance
It is that vacuum degree is reached less than 100Pa, then leads to protective atmosphere to 105Pa is repeated and is continued again after vacuumizing logical protective atmosphere 4-8 times
Logical protective atmosphere, is sintered ceramic body under protective atmosphere.
The principle of the present invention is：
The present invention passes through to SrTiO3The Ba of progress Sr is co-doped with Sm under the protective atmosphere sintering with reproducibility changes
Property, rare-earth Sm is donor doping, leads to Ti inside ceramics4+Ions binding free electron generates Ti3+Ion, a Ti3+Ion can
To be counted as a Ti4+One electronics (Ti of ion binding4+·e)；And the Lacking oxygen generated under protective atmosphere such as nitrogen sintering
It can also increase Ti with free electron3+The quantity of ion, a large amount of Ti3+The dipole for the stabilization that ion is formed with Lacking oxygen , since electronics is bound, therefore at a temperature of being activated less than electronics, the jump of electronics is this status for it
The jump set causes ceramics to have huge dielectric constant and low-dielectric loss；The Ba of ferroelectric phase enters paraelectric phase SrTiO simultaneously3, can
To tune the stability of dielectric properties, inhibit the relaxation phenomena because of dielectric loss peak caused by rear-earth-doped, and then can be real
The temperature and frequency stability of existing giant dielectric performance.
The beneficial effects of the invention are as follows：
1) present invention is by SrTiO3It carries out Sr Ba and Sm and is co-doped with modification, and carry out protective atmosphere sintering.It is making pottery
Form the dipole of a certain number of stabilizations inside porcelain, the movement to fetter free electron is obtained with huge dielectric constant and low
The SrTiO of dielectric loss3Base ceramic material；The material is in 0~300 DEG C (test frequency 1kHz) and 20Hz~20KHz (test temperature
Spend 50~200 DEG C of range) broad temperature, broadband under the conditions of have great dielectric constant (>20000) and low-dielectric loss (<0.05),
And there is excellent temperature and frequency stability.
2) by the different doping contents of change Ba, it can be obviously improved the dielectric constant of gained dielectric ceramic material,
The dielectric loss relaxation peak caused by rear-earth-doped is reduced, the dielectric properties stability of ceramic material is regulated and controled.
3) present invention has no special requirements to the granularity and grain size of raw material, and the doping of rare-earth Sm is micro and fixed, therefore
Production cost can be reduced；And the preparation method being related to is simple, reproducible, high yield rate, cost is relatively low, is convenient for business metaplasia
Production.
Description of the drawings
Fig. 1 is the Ba prepared by the embodiment of the present invention 10.2Sr0.77Sm0.02TiO3Prepared by ceramic material (1) and comparative example 5
Ba0.6Sr0.37Sm0.02TiO3The XRD spectrum of ceramic material (2).
Fig. 2 is the Ba prepared by the embodiment of the present invention 10.2Sr0.77Sm0.02TiO3The SEM spectrum of ceramic material.
Fig. 3 is the Ba prepared by the embodiment of the present invention 10.2Sr0.77Sm0.02TiO3The XPS collection of illustrative plates of ceramic material.
Fig. 4 is the Ba prepared by the embodiment of the present invention 10.2Sr0.77Sm0.02TiO3The impedance spectrum of ceramic material.
Fig. 5 is the Ba prepared by the embodiment of the present invention 10.2Sr0.77Sm0.02TiO3Ceramic material is within the scope of -60~400 DEG C
(a) dielectric constant with temperature change curve, (b) dielectric loss vary with temperature curve；It wherein follows the arrow the frequency in direction
Rate is respectively 0.1kHz, 1kHz, 10kHz, 100kHz.
Fig. 6 is the Ba prepared by inventive embodiments 10.2Sr0.77Sm0.02TiO3Ceramic material is within the scope of 20Hz~300kHz
(a) dielectric constant is with frequency variation curve, and (b) dielectric loss is with frequency variation curve；It wherein follows the arrow the temperature in direction
Respectively 50 DEG C, 100 DEG C, 150 DEG C, 200 DEG C.
Fig. 7 is the SrTiO prepared by comparative example 1 of the present invention3(a) dielectric of ceramic material within the scope of 20~400 DEG C is normal
Number varies with temperature curve, and (b) dielectric loss varies with temperature curve；The frequency in direction of wherein following the arrow is respectively
0.1kHz, 1kHz, 10kHz, 100kHz.
Fig. 8 is the Ba prepared by comparative example 2 of the present invention0.2Sr0.79TiO3(a) of the ceramic material within the scope of 20~400 DEG C
Dielectric constant with temperature change curve, (b) dielectric loss vary with temperature curve；Wherein follow the arrow direction frequency difference
For 0.1kHz, 1kHz, 10kHz, 100kHz.
Fig. 9 is the Ba prepared by comparative example 3 of the present invention0.2Sr0.77Sm0.02TiO3Ceramic material is within the scope of 20~400 DEG C
(a) dielectric constant with temperature change curve, (b) dielectric loss vary with temperature curve；It wherein follows the arrow the frequency in direction
Rate is respectively 0.1kHz, 1kHz, 10kHz, 100kHz.
Figure 10 is the Ba prepared by comparative example 5 of the present invention0.6Sr0.37Sm0.02TiO3Range of the ceramic material at 20~350 DEG C
Interior (a) dielectric constant with temperature change curve, (b) dielectric loss vary with temperature curve；It wherein follows the arrow direction
Frequency is respectively 0.1kHz, 1kHz, 10kHz, 100kHz.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment and attached drawing content that the present invention is furture elucidated, but this
The content of invention is not limited solely to the following examples.
Embodiment 1
A kind of dielectric ceramic material (Ba of huge dielectric constant low-dielectric loss0.2Sr0.77Sm0.02TiO3, marked as
BSST-28), preparation method includes the following steps：
1) with BaCO3、SrCO3、Sm2O3And TiO2For raw material, according to Ba0.2Sr0.77Sm0.02TiO3Stoichiometric ratio choose
Each raw material amounts to 30g, gained mixed raw material is fitted into ball grinder, uses zirconium ball and absolute ethyl alcohol as medium, ball milling speed is
900r/min, ball milling were put into drying box and dry after 24 hours, and drying box temperature is set as 100 DEG C, and drying time is 24 hours；
2) gained mixture pre-burning 2 hours under 1150 DEG C of air atmospheres after drying carry out the powder after pre-burning secondary
Ball milling obtains pre-burning powder, and secondary ball milling process is consistent with mechanical milling process described in step 1)；
3) pre-burning powder addition binder is granulated and is sieved, binder is the polyethylene that mass concentration is 5wt%
Alcoholic solution is 0.08 according to the ratio between binder volume and pre-burning powder quality:1(ml:G) ratio is ground in five times, is ground
The sieve that powder after mill crosses 100 mesh is granulated, obtain granularity 150~300um spherical powder；The powder warp being granulated
Cross it is aging for 24 hours after, it is dry-pressing formed (pressure 12MPa) with uniaxial tension, be made a diameter of 12mm, 0.7~1.2mm of thickness pottery
Porcelain billet body；Ceramic body is put in atmosphere furnace, in advance sintering furnace interior conduit is carried out being evacuated to system before sintering true
Reciprocal of duty cycle, which reaches, is less than 100Pa, then leads to nitrogen to 105Pa repeats after vacuumizing logical nitrogen 5 times maintaining nitrogen purge again, nitrogen stream
Speed is 70mL/min, is sintered in a nitrogen atmosphere to ceramic body, the actual temp system of sintering is：First with 5 DEG C/min
Heating rate be warming up to 1000 DEG C, then with the heating rate of 2 DEG C/min be warming up to 1500 DEG C and keep the temperature 2.5 hours, sintering
Ceramic temperature-fall period afterwards cools to after 1000 DEG C furnace cooling up to the huge dielectric constant low-dielectric loss with 2 DEG C/min
Dielectric ceramic material；During entire heating, heat preservation and cooling, nitrogen circulates in whole system always.
The present embodiment products therefrom is subjected to X-ray diffraction analysis, the result is shown in Figure 1.As seen from Figure 1, nitrogen atmosphere
BSST-28 ceramics under sintering are that single cubic perovskite structure has illustrated Ba and Sm without the generation of any second phase
It is dissolved into a cube SrTiO completely3In structure；The SEM figures of the present embodiment products therefrom are as shown in Figure 2.As seen from Figure 2, nitrogen
Ceramic dense micro-structure degree is preferable under gas sintering atmosphere, and crystallite dimension is relatively uniform, about 1.48 μm.
The XPS spectrum figure of Ti is as shown in figure 3, as seen from Figure 3 in the present embodiment products therefrom, Ti under nitrogen sintering atmosphere
2p3/2Peak can be fitted as Ti3+2p3/2And Ti4+2p3/2Obviously there is Ti in figure in peak3+2p3/2Peak shows
When BSST-28 ceramics are sintered in nitrogen, there is part Ti4+Ion is reduced into Ti3+Ion (Ti4+·e)；Pass through Ti3+And Ti4+
2p3/2The area at peak can substantially estimate the Ti of the lower BSST-28 samples of nitrogen atmosphere sintering3+The ratio of Ti ions shared by ion
Weigh about is 14.8%.A large amount of Ti3+Ion can form stable disfigurement model with Lacking oxygenIt is this
Dipole can effectively ensure that the huge dielectric constant and low-dielectric loss performance of products therefrom.
Fig. 4 is the impedance spectrum (measuring temperature is 400 DEG C) of BSST-28 ceramic materials obtained by the present embodiment, can be with by Fig. 4
To find out, the crystal grain of the lower gained ceramic material of nitrogen atmosphere sintering and the electric property otherness of crystal boundary are smaller, and the relaxation time is close,
Interfacial polarization is weaker.
Shown in Jie's thermogram 5 of BSST-28 ceramic materials.Jie's spectrogram of BSST-28 ceramic materials is as shown in Figure 6.By
Figure as can be seen that nitrogen atmosphere assisted sintering BSST-28 ceramic materials in the temperature at 0~300 DEG C (test frequency 1kHz)
Spend range in and 20Hz~20KHz (50~200 DEG C of Range of measuring temp) frequency range in have great dielectric constant (>
20000) and low-dielectric loss (<0.05), there is excellent temperature and frequency stability.Wherein be 25 DEG C in temperature is with frequency
Under conditions of 1kHz, the dielectric constant and dielectric loss that measure are respectively 26795 and 0.036.
Embodiment 2
A kind of dielectric ceramic material (Ba of huge dielectric constant low-dielectric loss0.4Sr0.57Sm0.02TiO3, marked as
BSST-46), preparation method is roughly the same with embodiment 1, is without place：By Ba0.4Sr0.57Sm0.02TiO3(BSST-
46) stoichiometric ratio chooses each raw material；Ball-milling Time is 30 hours, ball milling speed 800r/min；Drying box temperature is set as 100
DEG C, drying time is 30 hours；Calcined temperature is 1100 DEG C, and the time is 3 hours；The secondary ball milling time is 30h, ball milling speed
800r/min；Uniaxial tension is 10MPa；Persistently lead to nitrogen again after carrying out repeating to vacuumize logical nitrogen 4 times to sintering furnace interior conduit
Gas, nitrogen flow rate 100mL/min；The temperature schedule of sintering process is：First 1000 are warming up to the heating rate of 6 DEG C/min
DEG C, then with the heating rate of 3 DEG C/min be warming up to 1450 DEG C and keep the temperature 3 hours, it is sintered ceramics temperature-fall period with 3 DEG C/
Furnace cooling after min cools to 1000 DEG C.During entire heating, heat preservation and cooling, nitrogen circulates in entirely always
System.
The dielectric ceramic material of huge dielectric constant low-dielectric loss manufactured in the present embodiment is in 0~300 DEG C of (test frequency
There is huge Jie within the temperature range of 1kHz) and in the frequency range of 20Hz~20KHz (50~200 DEG C of Range of measuring temp)
Electric constant (>20000) and low-dielectric loss (<0.05), there is excellent temperature and frequency stability.Wherein 25 DEG C, 1kHz items
Under part, dielectric constant and dielectric loss are respectively 27341 and 0.048.
Embodiment 3
A kind of dielectric ceramic material (Ba of huge dielectric constant low-dielectric loss0.1Sr0.87Sm0.02TiO3, marked as
BSST-19), preparation method is roughly the same with embodiment 1, is without place：By Ba0.1Sr0.87Sm0.02TiO3(BSST-
19) stoichiometric ratio chooses each raw material；Ball-milling Time is 18 hours, ball milling speed 1000r/min；Calcined temperature is 1180
DEG C, the time is 2.5 hours；The secondary ball milling time is 18h, ball milling speed 1000r/min；Washing before carrying out nitrogen assisted sintering
During gas, continuously repeats and continue to lead to nitrogen in entire pipeline with the rate of 50mL/min after vacuumizing logical nitrogen 8 times, in nitrogen
Ceramic body is sintered under gas atmosphere obtained；The actual temp system of sintering process is：First with the heating rate of 8 DEG C/min
1000 DEG C are warming up to, be then warming up to 1550 DEG C with the heating rate of 5 DEG C/min and keeps the temperature 2 hours, sintered ceramics cooling
Furnace cooling after process cools to 1000 DEG C with 5 DEG C/min.During entire heating, heat preservation and cooling, nitrogen is always
Circulate in whole system.
In the dielectric ceramic material of huge dielectric constant low-dielectric loss manufactured in the present embodiment, in 0~300 DEG C of (test
Frequency 1kHz) within the temperature range of and 20Hz~20KHz (50~200 DEG C of Range of measuring temp) frequency range in have it is huge
Big dielectric constant (>20000) and low-dielectric loss (<0.05), there is excellent temperature and frequency stability.Wherein 25 DEG C,
Under the conditions of 1kHz, dielectric constant and dielectric loss are respectively 23527 and 0.042.
Comparative example 1
By SrCO3And TiO2According to SrTiO3Stoichiometric ratio proportioning mixing, outfits raw material mixture gross weight be 30g.It will
Raw mixture uses zirconium ball and absolute ethyl alcohol as medium, and ball milling speed 900r/min, ball milling is dried after 24 hours, after drying
Mixture under 1150 DEG C of air atmospheres pre-burning 2 hours.5wt% is added in powder after pre-burning after secondary ball milling for 24 hours
Poly-vinyl alcohol solution is granulated and is sieved, dry-pressing formed (pressure 12MPa), and obtained a diameter of 12mm, thickness 0.7~
The ceramic body of 1.2mm.It is warming up to 1000 DEG C in nitrogen atmosphere with the heating rate of 5 DEG C/min, then with 2 DEG C/min
Heating rate be warming up to 1500 DEG C and keep the temperature 2.5 hours, after temperature-fall period cools to 1000 DEG C with 2 DEG C/min furnace cooling obtain
To the SrTiO of sintering3Ceramic material, unmentioned part is identical as the condition of embodiment 1 in whole preparation process.
SrTiO prepared by this comparative example3Ceramics carry out dielectric properties test, and the temperature that is situated between spectrum is as shown in fig. 7, by scheming
It arrives：Under the conditions of 25 DEG C, 1kHz, dielectric constant and dielectric loss are respectively 295 and 0.0052, and dielectric constant is significantly lower than this
Invent the SrTiO that the Ba and Sm carry out Sr substitutions jointly3Base giant dielectric ceramic material (embodiment 1).
Comparative example 2
By SrCO3、BaCO3、TiO2According to Ba0.2Sr0.79TiO3Stoichiometric ratio proportioning mixing, be equipped with raw material mixture
Gross weight is 30g.To use zirconium ball and absolute ethyl alcohol as medium raw mixture, ball milling speed 900r/min, ball milling 24 is small
When after dry, pre-burning 2 hours under 1150 DEG C of air atmospheres of the mixture after drying.Powder after pre-burning is secondary by for 24 hours
5wt% poly-vinyl alcohol solutions are added after ball milling to be granulated and be sieved, it is dry-pressing formed (pressure 12MPa), it is made a diameter of
The ceramic body of 12mm, 0.7~1.2mm of thickness.It is warming up to 1000 in nitrogen atmosphere with the heating rate of 5 DEG C/min
DEG C, then 1500 DEG C being warming up to the heating rate of 2 DEG C/min and keeping the temperature 2.5 hours, temperature-fall period is cooled to 2 DEG C/min
The Ba that furnace cooling is sintered after 1000 DEG C0.2Sr0.79TiO3Ceramic material, unmentioned part is equal in whole preparation process
It is identical as the condition of embodiment 1.To the Ba of preparation0.2Sr0.79TiO3Ceramics carry out dielectric properties test, and the temperature that is situated between spectrum is such as Fig. 8 institutes
Show, as seen from the figure：Under the conditions of 25 DEG C, 1kHz, dielectric constant and dielectric loss are respectively 274 and 0.0069, dielectric constant
Carry out the SrTiO of Sr substitutions jointly significantly lower than Ba of the present invention and Sm3Base giant dielectric ceramic material (embodiment 1).
Comparative example 3
By BaCO3、SrCO3、Sm2O3And TiO2As raw material according to Ba0.2Sr0.77Sm0.02TiO3Stoichiometric ratio proportioning
Mixing, outfit raw material mixture gross weight are 30g.To use zirconium ball and absolute ethyl alcohol as medium, ball milling speed raw mixture
For 900r/min, ball milling is dried after 24 hours, pre-burning 2 hours under 1150 DEG C of air atmospheres of the mixture after drying.After pre-burning
Powder 5wt% poly-vinyl alcohol solutions are added after secondary ball milling are for 24 hours granulated and are sieved, it is dry-pressing formed that (pressure is
12MPa), the ceramic body of a diameter of 12mm, 0.7~1.2mm of thickness is made, and is sintered under oxygen atmosphere.To sintering furnace
Interior conduit carries out persistently leading to oxygen, oxygen gas flow rate 70mL/min, by it in oxygen atmosphere again after repeating to vacuumize logical oxygen 5 times
In with the heating rate of 5 DEG C/min be warming up to 1000 DEG C, be then warming up to 1500 DEG C with the heating rate of 2 DEG C/min and keep the temperature
2.5 hours, temperature-fall period cooled to the Ba that furnace cooling is sintered after 1000 DEG C with 2 DEG C/min0.2Sr0.77Sm0.02TiO3Pottery
Ceramic material, unmentioned part is identical as the condition of embodiment 1 in whole preparation process.To preparation
Ba0.2Sr0.77Sm0.02TiO3Ceramics carry out dielectric properties test, and the temperature that is situated between spectrum by figure as shown in figure 9, obtained：In 25 DEG C, 1kHz
Under the conditions of, dielectric constant and dielectric loss are respectively 576 and 0.013, and dielectric constant is significantly lower than Ba of the present invention and Sm
The common SrTiO for carrying out Sr substitutions3Base giant dielectric ceramic material (embodiment 1).
Comparative example 4
By BaCO3、SrCO3、Sm2O3And TiO2As raw material according to Ba0.2Sr0.77Sm0.02TiO3Stoichiometric ratio proportioning
Mixing, outfit raw material mixture gross weight are 30g.To use zirconium ball and absolute ethyl alcohol as medium, ball milling speed raw mixture
For 900r/min, ball milling is dried after 24 hours, pre-burning 2 hours under 1150 DEG C of air atmospheres of the mixture after drying.After pre-burning
Powder 5wt% poly-vinyl alcohol solutions are added after secondary ball milling are for 24 hours granulated and are sieved, it is dry-pressing formed that (pressure is
12MPa), the ceramic body of a diameter of 12mm, 0.7~1.2mm of thickness is made.By it with the liter of 10 DEG C/min in nitrogen atmosphere
Warm rate is warming up to 1000 DEG C, and being then warming up to 1580 DEG C with the heating rate of 5 DEG C/min keeps the temperature 2 hours, and temperature-fall period is direct
The Ba that furnace cooling is sintered0.2Sr0.77Sm0.02TiO3Ceramic material, in whole preparation process unmentioned part with
The condition of embodiment 1 is identical.To the Ba of preparation0.2Sr0.77Sm0.02TiO3Ceramics carry out dielectric properties test, obtain：25 DEG C,
Under the conditions of 1kHz, dielectric constant and dielectric loss are respectively 9817 and 0.067, and dielectric constant is significantly lower than Ba of the present invention
Carry out the SrTiO of Sr substitutions jointly with Sm3Base giant dielectric ceramic material (embodiment 1), dielectric loss is apparently higher than the present invention
The Ba and Sm carries out the SrTiO of Sr substitutions jointly3Base giant dielectric ceramic material (embodiment 1).This explanation is in nitrogen atmosphere
Middle sintering, the setting of sintering temperature and the control of cooling process are affected to the dielectric properties of ceramics.
Comparative example 5
By BaCO3、SrCO3、Sm2O3And TiO2As raw material according to Ba0.6Sr0.37Sm0.02TiO3Stoichiometric ratio proportioning
Mixing, outfit raw material mixture gross weight are 30g.To use zirconium ball and absolute ethyl alcohol as medium, ball milling speed raw mixture
For 900r/min, ball milling is dried after 24 hours, pre-burning 2 hours under 1150 DEG C of air atmospheres of the mixture after drying.After pre-burning
Powder 5wt% poly-vinyl alcohol solutions are added after secondary ball milling are for 24 hours granulated and are sieved, it is dry-pressing formed that (pressure is
12MPa), the ceramic body of a diameter of 12mm, 0.7~1.2mm of thickness is made.By it with the liter of 5 DEG C/min in nitrogen atmosphere
Warm rate is warming up to 1000 DEG C, is then warming up to 1500 DEG C with the heating rate of 2 DEG C/min and keeps the temperature 2.5 hours, temperature-fall period
The Ba that furnace cooling is sintered after 1000 DEG C is cooled to 2 DEG C/min0.6Sr0.37Sm0.02TiO3Ceramic material is entirely being prepared
Unmentioned part is identical as the condition of embodiment 1 in the process.
This comparative example products therefrom is shown in Fig. 1 through XRD characterization analysis result：Its structure is that the division of diffraction maximum occurs, knot
Structure is changed by the opposite ferroelectric phase of para-electric.To the Ba of preparation0.6Sr0.37Sm0.02TiO3Ceramics carry out dielectric properties test, the temperature that is situated between spectrum
As shown in Figure 10, it is obtained by figure：Under the conditions of 25 DEG C, 1kHz, dielectric constant and dielectric loss are respectively 13789 and 0.38,
Its dielectric constant carries out the SrTiO of Sr substitutions significantly lower than Ba of the present invention and Sm jointly3Base giant dielectric ceramic material is (real
Apply example 1), dielectric loss is apparently higher than the SrTiO that Ba and Sm of the present invention carry out Sr substitutions jointly3Base giant dielectric ceramics material
Expect (embodiment 1).This illustrates that the doping of Ba is excessive, and ceramic structure can change, and be affected to dielectric properties.
By comparing embodiment 1 with comparative example 1 and 2 it is found that Ba and Sm co-dopeds are affected to giant dielectric performance, and
Protective atmosphere is sintered and reasonably sintering temperature and doping can all have an impact dielectric properties.
By studying different component doping, different atmosphere sintering and different temperatures sin-tering mechanism, to the ceramic material of preparation
Material has carried out the investigation of dielectric properties, the experimental results showed that：Ba and Sm of the present invention carry out jointly Sr substitution
SrTiO3Base ceramic material is sintered the ceramics that the huge dielectric constant low-dielectric loss under broad temperature, broadband can be obtained under protective atmosphere
Material, and the preparation method being related to is simple, reproducible, at low cost, high yield rate.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, belong to the protection of the present invention
Range.
Claims (10)
1. a kind of dielectric ceramic material of huge dielectric constant low-dielectric loss, which is characterized in that it is common using Ba and Sm
Carry out the SrTiO of Sr substitutions3Base giant dielectric ceramic material, general formula BaxSr0.97-xSm0.02TiO3, the value model of wherein x
It encloses for 0.1≤x≤0.4, the doping of Sm is fixed as 0.02.
2. the preparation method of the dielectric ceramic material of huge dielectric constant low-dielectric loss according to claim 1, special
Sign is, includes the following steps：
1) with SrCO3、Sm2O3、TiO2And BaCO3For raw material, by BaxSr0.97-xSm0.02TiO3Stoichiometric ratio weighed,
Gained mixed raw material is carried out ball milling, drying by mixing；
2) drying product progress pre-burning, secondary ball milling obtained by step 1) are obtained into pre-burning powder, then adds binder granulation and goes forward side by side
Ceramic body is obtained after row sieving, compression moulding, dumping；
3) gained ceramic body is placed under protective atmosphere and is sintered, the cooling obtained huge dielectric constant low-dielectric loss
Dielectric ceramic material.
3. preparation method according to claim 2, which is characterized in that the ball milling speed of the ball milling and secondary ball milling process
For 800~1000r/min, Ball-milling Time is 18~30 hours.
4. preparation method according to claim 2, which is characterized in that the calcined temperature is 1100~1180 DEG C, pre-burning
Soaking time is 2~4h.
5. preparation method according to claim 2, which is characterized in that sintering process described in step 3) is：With 4~8 DEG C/
The rate of min is heated to 900~1000 DEG C, is then warming up to 1400~1550 DEG C of heat preservation sinterings 2 with the rate of 2~5 DEG C/min
~4h, then 900~1100 DEG C are cooled to the rate of 2~5 DEG C/min, finally with stove natural cooling.
6. preparation method according to claim 2, which is characterized in that the binder is polyvinyl alcohol water solution, quality
A concentration of 2.5~5wt%.
7. preparation method according to claim 2, which is characterized in that the quality of the binder volume and pre-burning powder it
Than for (0.04~0.08) ml:1g.
8. preparation method according to claim 2, which is characterized in that the pressure that the compression moulding process uses for 10~
15Mpa。
9. preparation method according to claim 2, which is characterized in that the stream of protective atmosphere in the step 3) sintering process
Logical rate is 50~100mL/min, and protective atmosphere is nitrogen or argon gas.
10. preparation method according to claim 2, which is characterized in that right in advance before carrying out the step 3) sintering process
Sintering furnace interior conduit be evacuated to system vacuum degree and reach being less than 100Pa, then leads to protective atmosphere to 105Pa repeats pumping
Vacuum leads to after protective atmosphere 4-8 time again persistently logical protective atmosphere, is sintered to ceramic body under protective atmosphere.
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