CN106854079A - Microwave-medium ceramics, the preparation method and application of temperature coefficient of resonance frequency nearly zero - Google Patents
Microwave-medium ceramics, the preparation method and application of temperature coefficient of resonance frequency nearly zero Download PDFInfo
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Abstract
The invention discloses a kind of microwave-medium ceramics of temperature coefficient of resonance frequency nearly zero, belong to microwave dielectric ceramic materials field, microwave-medium ceramics formula composition falls in xTiO2‑y(Zn1/ 3Nb2/3)O2‑(100‑x‑y)ZrO2In the setting compositing area of ternary system, setting regions refers to the closed area of nine line segments composition according to sequencing successively head and the tail connection in ternary system.The microwave-medium ceramics of temperature coefficient of resonance frequency of the invention nearly zero can be used to prepare mobile communication base station dielectric filter, resonator and antenna.The invention also discloses the preparation method of the microwave-medium ceramics for preparing the temperature coefficient of resonance frequency nearly zero.According to the present invention, the relatively low formula of Costco Wholesale can be flexibly matched in the range of large area, prepare the media ceramic of temperature coefficient of resonance frequency nearly zero.
Description
Technical field
The invention belongs to microwave dielectric ceramic materials field, more particularly, to a kind of temperature coefficient of resonance frequency nearly zero
TiO2-(Zn1/3Nb2/3)O2-ZrO2It is microwave dielectric ceramic and application.
Background technology
Microwave technology is one of great achievement of modern science development.Because microwave has the advantages that wavelength is short, frequency is high,
Thus there is good selecting frequency characteristic, be widely used in the detecting devices such as radar, for locating and tracking target.Into 21 century with
Come, electronic system is widely used, the foundation of 4G networks, microwave technology has been obtained more vigorous growth.At this
Under the promotion of technical background, people make pottery in the urgent need to the microwave-medium with low-dielectric loss, near-zero resonance frequency temperature coefficient
Ceramic material.And microwave-medium ceramics as the critical material of mobile communication base station, it is necessary to keep frequency-selecting under temperature control
Stability, this just makes ceramic material temperature coefficient of resonance frequency nearly zero seem increasingly important.
ZrO2-TiO2System's ceramics are a kind of microwave dielectric ceramic materials of function admirable.Wherein ZrTiO4Ceramics have higher
Dielectric constant and quality factor higher, its dielectric constant is up to 42, and quality factor are up to 28000GHz, are extraordinary shiftings
The candidate material of dynamic communication base station wave filter.But, it (is 56ppm/ that the absolute value of the ceramic temperature coefficient of resonance frequency is larger
DEG C), and sintering temperature is higher, which prevent ZrTiO4Application of the ceramics on the wave filter of mobile communication base station.And columbite
The ZnNb of structure2O6Ceramics have relatively low sintering temperature and more excellent microwave dielectric property：Its dielectric constant is 25, product
Prime factor is up to 83700GHz, but, the ceramic temperature coefficient of resonance frequency is -56ppm/ DEG C.Advised according to Li Hedeniekai
Then, a kind of microwave dielectric material of positive temperature coefficient of resonance frequency is selected with a kind of microwave-medium of negative temperature coefficient of resonance frequency
Material is combined, and the temperature coefficient of resonance frequency of composite can be adjusted into 0ppm/ DEG C.
RiaziKhoei et al. 2006 is in Journal of the American Ceramic Society, 89 (1):
Paper has been delivered on 216-223《The Influence of ZnNb2O6on the microwave dielectric
properties of ZrTi2O6ceramics》, study in ZnNb2O6-ZrTi2O6Change ZnNb in binary system2O6With
ZrTi2O6Influence of the ratio to ceramic microwave dielectric properties.The research has the following disadvantages：(1) model is changed in very big composition
In enclosing, only in 0.24ZnNb2O6-0.76ZrTi2O6Composition, the temperature coefficient of resonance frequency nearly zero of ceramics；(2) ceramic systems
Need to be sintered in oxygen atmosphere, hinder its commercialized development.
Tang Bin et al. 2013 is in Journal of Materials Science:Materials in
Electronics,24(5):Delivered on 1475-1479 entitled《Phase structure and microwave
dielectric properties of Zr(Zn1/3Nb2/3)xTi2-xO6(0.2≤x≤0.8)ceramics》Article, Wen Zhong
In the case of constant Zr contents, change (Zn1/3Nb2/3) with the ratio of Ti, but exist substantially not enough：Become in very big composition
In the range of change, only in the composition of x=0.4, the temperature coefficient of resonance frequency nearly zero of ceramics.
Liao Qing for et al. 2012 in Solid State Sciences, 14 (9):Delivered on 1385-1391《Phase
constitution structure analysis and microwave dielectric properties of
Zn0.5Ti1-xZrxNbO4ceramics》Article, text in constant (Zn1/3Nb2/3) in the case of content, change the ratio of Zr and Ti
Example, but exist substantially not enough：Only in the composition of x=0.6, the temperature coefficient of resonance frequency of ceramics is -15.5ppm/ DEG C.
Cui causes remote et al. 2014 in Journal of Electronic Materials, 2015,44 (1):320-325
It is upper to deliver《Influence of Zr/Ti Ratio on the Microwave Dielectric Behavior of
xZrO2-0.4(Zn1/3Nb2/3)O2-yTiO2Ceramics》Article, in constant (Zn in text1/3Nb2/3) in the case of content, change
The ratio of Zr and Ti, but exist substantially not enough：Wherein, only in the composition that Zr/Ti is 8/8 and 7/9, the resonant frequency temperature of ceramics
Degree coefficient nearly zero, the compositing area that it meets temperature coefficient of resonance frequency nearly zero is narrower.
Publication No. has been the U.S. Patent Application Publication of US005470808A, and one group of raw material proportioning is xTiO2-y(Zn1/ 3Nb2/3)O2-zZrO2The microwave-medium ceramics of (x ∈ (0.1,0.6), y ∈ (0.2,0.6), z ∈ (0.01,0.7)) and its preparation
Method.Although the system have studied its microwave dielectric property in larger ratio range, exist following not enough：(1) only exist
54TiO2-34(Zn1/3Nb2/3)O2-14ZrO2,40TiO2-20(Zn1/3Nb2/3)O2-40ZrO2,45TiO2-25(Zn1/3Nb2/3)O2-
35ZrO2Three compositions, the temperature coefficient of resonance frequency nearly zero of ceramics；(2) sintering temperature is burnt all between 1300-1650 DEG C
Junction temperature is too high, hinders its commercialized development.
In the U.S. Patent application, 40TiO2-20(Zn1/3Nb2/3)O2-40ZrO2With 45TiO2-25(Zn1/3Nb2/3)O2-
35ZrO2Composition and Cui Zhiyuan et al. in paper《Influence of Zr/Ti Ratio on the Microwave
Dielectric Behavior of x ZrO2-0.4(Zn1/3Nb2/3)O2-yTiO2Ceramics》Middle Zr/Ti is 8/8 and 7/9
Composition it is identical.
Sum it up, in the prior art, TiO2-(Zn1/3Nb2/3)O2-ZrO2It is ceramic resonance frequency-temperature coefficient nearly zero
Formula composition is all very limited, and region is narrower, causes have more limitation in practical engineering application, flexibly choosing of also having no idea
It is selected to point and control material cost.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of temperature coefficient of resonance frequency nearly zero
Microwave-medium ceramics, its preparation method and application, its object is to provide a series of matching somebody with somebody for temperature coefficient of resonance frequencies nearly zero
Fang Zucheng, formula composition can meet requirement of the mobile communication base station to ceramic resonance frequency-temperature coefficient so that in reality
In engineer applied, the composition of material can be flexibly matched in the range of large area, the formula of low in raw material price can be selected, and
Preparation method process is simple, low production cost.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of temperature coefficient of resonance frequency nearly zero
Microwave-medium ceramics, the microwave-medium ceramics formula composition falls within xTiO2-y(Zn1/3Nb2/3)O2-(100-x-y)ZrO2Ternary
In the compositing area of system setting,
The compositing area of the setting refer in the ternary system nine line segments according to sequencing successively head and the tail connection
The closed area of composition,
Nine line segments are nine line segments in the following order,
First line segment：X-y=-7.8, wherein, y=30.99~33.14；
Article 2 line segment：X+y=58.48, wherein, y=21.52~33.14；
Article 3 line segment：X-2.65y=-20.07, wherein, y=21.52~25.73；
Article 4 line segment：2.46x+y=144.1, wherein, y=25.73~69.83；
Article 5 line segment：X+y=100, wherein y=63.52-69.83；
Article 6 line segment：2.45x+y=152.8, wherein, y=23.10~63.52；
Article 7 line segment：7.74x+y=432.39, wherein, y=13.5~23.10；
Article 8 line segment：X-1.525y=33.54, wherein, y=7.86~13.5；
Article 9 line segment：X+0.966y=53.11, wherein, y=7.86~30.99；
Wherein, x, y and (100-x-y) are respectively TiO in ternary system2、(Zn1/3Nb2/3)O2And ZrO2Molar percentage contains
Amount, unit is mol%.
According to one aspect of the present invention, the microwave-medium pottery of temperature coefficient of resonance frequency as described above nearly zero is also provided
The application of porcelain.
Further, it is used to prepare mobile communication base station dielectric filter, resonator and antenna.
According to the third aspect of the invention, there is provided a kind of microwave-medium ceramics of temperature coefficient of resonance frequency nearly zero, institute
State microwave-medium ceramics formula composition and fall within xTiO2-y(Zn1/3Nb2/3)O2-(100-x-y)ZrO2The setting composition of ternary system
In line segment, wherein,
First line segment：3 (x-40)=8 (y-20), wherein, y=16~25；
Article 2 line segment：20 (x-44.17)=- 8.13 (y-20), wherein, y=29.56~66.67；
Article 3 line segment：3 (x+y)=169, wherein, y=19~37.66；
Article 4 line segment：123x=-112 (y-60), wherein, (y=6.7~19)；
Article 5 line segment：15 (x-52)=- 2 (y-14), wherein, (y=14~24)；
Article 6 line segment：15 (x-52)=- 44 (y-14), wherein, (y=15~19)；
Wherein, x, y and (100-x-y) are respectively TiO in ternary system2、(Zn1/3Nb2/3)O2And ZrO2Molar percentage contains
Amount, unit is mol%.
According to the fourth aspect of the invention, a kind of microwave-medium of described temperature coefficient of resonance frequency nearly zero is also provided
The application of ceramics.It is applied to prepare mobile communication base station dielectric filter, resonator and antenna.
According to the fifth aspect of the invention, a kind of temperature coefficient of resonance frequency as described above nearly zero for preparing also is provided
The method of microwave-medium ceramics, it is characterised in that
First, by ZnO, Nb2O5、TiO2、ZrO2And the mixing of CuO powder,
Then, deionized water is added, ball milling obtains uniform mixture,
Then, mixture is dried, in 950 DEG C~1050 DEG C pre-burning 3h~4h,
Again, deionized water is added, secondary ball milling obtains uniform mixture,
Followed by, base substrate will be pressed into after mixture drying, granulation and sieving,
Finally, 3h~4h will be sintered after base substrate dumping at 1260 DEG C~1300 DEG C, obtains temperature coefficient of resonance frequency near
Zero ceramic material.
Further, the mass percentage content of CuO is ZnO, Nb2O5、ZrO2And TiO2Powder gross mass
0.5wt.%~1.0wt.%, preferably 0.5wt.%.
Further, use powder compressing machine to be suppressed to obtain base substrate, powder compressing machine briquetting pressure be 50MPa~
100Mpa。
Further, a diameter of 15mm of base substrate, the thickness of base substrate is 7.5mm.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show
Beneficial effect：
The invention provides a series of formula composition of temperature coefficient of resonance frequencies nearly zero, formula composition can meet shifting
Dynamic requirement of the communication base station to ceramic resonance frequency-temperature coefficient so that in practical engineering application, can be in large area scope
The composition of interior flexible apolegamy material, can select the formula of low in raw material price such that it is able to control material cost so that its is big
Production mobile communication base station wave filter is applied to scale to be possibly realized.
Preparation method process is simple of the invention, low production cost, further such that microwave-medium ceramics of the invention can
Large-scale commercial application.
Brief description of the drawings
Fig. 1 is the TiO of temperature coefficient of resonance frequency nearly zero in the present invention2-(Zn1/3Nb2/3)O2-ZrO2Ternary system ceramics
Compositing area schematic diagram, the resonant frequency temperature of all formula composition ceramics in irregular figure region in the ternary composition diagram
Coefficient nearly zero；
Fig. 2 is also the TiO of temperature coefficient of resonance frequency nearly zero in the present invention2-(Zn1/3Nb2/3)O2-ZrO2Ternary system is made pottery
Porcelain compositing area schematic diagram, the temperature coefficient of resonance frequency of all formula composition ceramics on six line segments in the ternary composition diagram
Nearly zero；
Fig. 3 is six kinds of X-ray diffractograms (XRD) of formula composition ceramics in First Series embodiment of the present invention；
Fig. 4 is eight kinds of X-ray diffractograms (XRD) of formula composition ceramics in second series embodiment of the present invention；
Fig. 5 is five kinds of X-ray diffractograms (XRD) of formula composition ceramics in the 3rd series embodiment of the invention；
Fig. 6 is three kinds of X-ray diffractograms (XRD) of formula composition ceramics in the 4th series embodiment of the invention；
Fig. 7 is four kinds of X-ray diffractograms (XRD) of formula composition ceramics in the 5th series embodiment of the invention；
Fig. 8 is four kinds of X-ray diffractograms (XRD) of formula composition ceramics in the 6th series embodiment of the invention；
Fig. 9 is the scanned photograph figure (SEM figures) that numbering is 1-1 formula composition ceramics in First Series embodiment of the present invention；
Figure 10 is the scanned photograph figure (SEM figures) that numbering is 1-2 formula composition ceramics in First Series embodiment of the present invention；
Figure 11 is the scanned photograph figure (SEM figures) that numbering is 1-3 formula composition ceramics in First Series embodiment of the present invention；
Figure 12 is the scanned photograph figure (SEM figures) that numbering is 1-4 formula composition ceramics in First Series embodiment of the present invention；
Figure 13 is the scanned photograph figure (SEM figures) that numbering is 1-5 formula composition ceramics in First Series embodiment of the present invention；
Figure 14 is the scanned photograph figure (SEM figures) that numbering is 1-6 formula composition ceramics in First Series embodiment of the present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method
Not constituting conflict each other can just be mutually combined.
Fig. 1 is the TiO of temperature coefficient of resonance frequency nearly zero in the present invention2-(Zn1/3Nb2/3)O2-ZrO2Ternary system ceramics
Formula compositing area schematic diagram, the microwave-medium ceramics formula composition falls within xTiO2-y(Zn1/3Nb2/3)O2-(100-x-y)
ZrO2In the setting compositing area of ternary system, the compositing area of the setting refer in the ternary system nine line segments according to elder generation
Head and the tail are connected and the closed area of composition order successively afterwards, and nine line segments are nine line segments in the following order：
First line segment：X-y=-7.8, wherein, y=30.99~33.14；
Article 2 line segment：X+y=58.48, wherein, y=21.52~33.14；
Article 3 line segment：X-2.65y=-20.07, wherein, y=21.52~25.73；
Article 4 line segment：2.46x+y=144.1, wherein, y=25.73~69.83；
Article 5 line segment：X+y=100, wherein y=63.52-69.83；
Article 6 line segment：2.45x+y=152.8, wherein, y=23.10~63.52；
Article 7 line segment：7.74x+y=432.39, wherein, y=13.5~23.10；
Article 8 line segment：X-1.525y=33.54, wherein, y=7.86~13.5；
Article 9 line segment：X+0.966y=53.11, wherein, y=7.86~30.99；
Wherein, x, y and (100-x-y) are respectively TiO in ternary system2、(Zn1/3Nb2/3)O2And ZrO2Molar percentage contains
Amount, unit is mol%.The ceramics that all formula compositions fall described in the ternary composition diagram in closed area, its resonant frequency
Temperature coefficient nearly zero.
Fig. 2 is also the TiO of temperature coefficient of resonance frequency nearly zero in the present invention2-(Zn1/3Nb2/3)O2-ZrO2Ternary system is made pottery
Porcelain compositing area schematic diagram, the microwave-medium ceramics formula composition falls within xTiO2-y(Zn1/3Nb2/3)O2-(100-x-y)ZrO2
On the setting line segment of ternary system, wherein,
First line segment：3 (x-40)=8 (y-20), wherein, y=16~25；
Article 2 line segment：20 (x-44.17)=- 8.13 (y-20), wherein, y=29.56~66.67；
Article 3 line segment：3 (x+y)=169, wherein, y=19~37.66；
Article 4 line segment：123x=-112 (y-60), wherein, (y=6.7~19)；
Article 5 line segment：15 (x-52)=- 2 (y-14), wherein, (y=14~24)；
Article 6 line segment：15 (x-52)=- 44 (y-14), wherein, (y=15~19)；
Wherein, x, y and (100-x-y) are respectively TiO in ternary system2、(Zn1/3Nb2/3)O2And ZrO2Molar percentage contains
Amount, unit is mol%.All formulas constitute the ceramics on six line segments in the ternary composition diagram, its resonant frequency temperature
Coefficient nearly zero.
In the present invention, the TiO of temperature coefficient of resonance frequency nearly zero is prepared2-(Zn1/3Nb2/3)O2-ZrO2The side of ternary ceramics
Method is as follows：
According to the fifth aspect of the invention, a kind of temperature coefficient of resonance frequency as described above nearly zero for preparing also is provided
The method of microwave-medium ceramics, it is characterised in that
First, by ZnO, Nb2O5、TiO2、ZrO2And the mixing of CuO powder, the mass percentage content of CuO is ZnO,
Nb2O5、ZrO2And TiO20.5wt.%~the 1.0wt.% of powder gross mass, preferably 0.5wt.%,
Then, deionized water is added, ball milling obtains uniform mixture,
Then, mixture is dried, in 950 DEG C~1050 DEG C pre-burning 3h~4h,
Again, deionized water is added, secondary ball milling obtains uniform mixture,
Followed by, base substrate will be pressed into after mixture drying, granulation and sieving, use powder compressing machine to be suppressed to obtain
Base substrate is obtained, powder compressing machine briquetting pressure is 50MPa~100Mpa.A diameter of 15mm of base substrate, the thickness of base substrate is 7.5mm,
Finally, 3h~4h will be sintered after base substrate dumping at 1260 DEG C~1300 DEG C, obtains temperature coefficient of resonance frequency near
Zero ceramic material.
For more detailed description the inventive method and the composition and performance of microwave-medium ceramics, with reference to specific
Embodiment is further illustrated.
First Series embodiment
This series embodiment is had altogether including six kinds of compositions, and numbering is 1-1,1-2,1-3,1-4,1-5 and 1-6 respectively.Tool
The composition of body refers to table 1.
By the ZnO that purity is more than 99.7%, purity is more than 99.99% ZrO2, purity is more than 99.84%
TiO2, purity is more than 99.99% Nb2O5With the CuO that purity is more than 99.5%, by 3 (x-40)=8 (y-20) (y=16-
25) dispensing is carried out, ball milling 1h is sufficiently mixed raw material.It is warming up to the speed of 300 DEG C/h in alumina crucible after drying
950 DEG C of pre-burning 4h, can also be warming up to 980 DEG C of pre-burning 3h, can also be warming up to 1000 DEG C of pre-burning 3.5h, can also be warming up to
1050 DEG C of pre-burning 4h.
By the powder wet ball-milling 1h after pre-burning, it is well mixed, obtains mixed-powder, its TiO2,(Zn1/3Nb2/3)
O2,ZrO2Mole percent level and CuO mass percentage content corresponding table 1 embodiment 1-1 to 1-6；By mixed-powder
After drying, 60 mesh sieves are granulated and crossed；Powder agglomerates after sieving are pressed into base substrate, its a diameter of 15mm is highly
7.5mm, when pressing blank, the pressure of embodiment 1-1,1-2 is 50MPa, and the pressure of 1-3 is 60MPa, and the pressure of 1-4 is
The pressure of 75MPa, 1-5 is 85MPa, and the pressure of 1-6 is 100MPa.Base substrate in air atmosphere, is heated up with the speed of 2 DEG C/min
To 550 DEG C, the dumping 0.5h at 550 DEG C is warming up to 1280 DEG C and sinters 4h after dumping with the speed of 300 DEG C/h, then cold with stove
But to room temperature, the ceramic material of temperature coefficient of resonance frequency nearly zero is obtained.
Wherein, the pre-sinter process of embodiment 1-1 to 1-6 is：With the speed liter of 300 DEG C/h in alumina crucible after drying
Temperature is to 950 DEG C of pre-burning 4h；980 DEG C of pre-burning 3h are warming up to the speed of 300 DEG C/h in alumina crucible after drying, after drying
1000 DEG C of pre-burning 3.5h are warming up to the speed of 300 DEG C/h in alumina crucible, with 300 DEG C/h in alumina crucible after drying
Speed be warming up to 1050 DEG C of pre-burning 4h；980 DEG C of pre-burnings are warming up to the speed of 300 DEG C/h in alumina crucible after drying
3.5h；950 DEG C of pre-burning 4h are warming up to the speed of 300 DEG C/h in alumina crucible after drying.
Wherein, the ball mill used by ball milling is planetary ball mill, and ball-milling medium is zirconium ball and deionized water；Granulation is used
Binding agent use mass concentration for 8% polyvinyl alcohol water solution, dosage for mixed-powder gross mass 6%.
Second series embodiment
This series embodiment is had altogether including eight kinds of compositions, respectively numbering be 2-1,2-2,2-3,2-4,2-5,2-6,2-7 with
And 2-8.Specific composition refers to table 1.
By the ZnO that purity is more than 99.7%, purity is more than 99.99% ZrO2, purity is more than 99.84%
TiO2, purity is more than 99.99% Nb2O5With the CuO that purity is more than 99.5%, by the 20 (y- of (x-44.17)=- 8.13
20) (y=29.56-66.67) carries out dispensing, its TiO2,(Zn1/3Nb2/3)O2,ZrO2Mole percent level and CuO matter
The embodiment numbering 2-1 to 2-8 of amount degree corresponding table 1, tableting pressure is 50MPa, and calcined temperature is 1000 DEG C, pre-burning
Time is 4h.1340 DEG C of the sintering temperature of wherein 2-1 to 2-5, the sintering temperature of 2-6 is 1300 DEG C of sintering 3h, the sintering temperature of 2-7
Spend for the sintering temperature of 1260 DEG C of sintering 3.5h, embodiment 2-8 is 1160 DEG C.Other parts are same as Example 1.
In this series embodiment, the quality hundred of CuO in embodiment 2-1,2-2,2-3,2-4,2-5,2-6,2-7 and 2-8
It is ZnO, Nb to divide than content2O5、ZrO2And TiO2The 0.5wt.% of powder gross mass, 0.6wt.%, 0.6wt.%,
0.7wt.%, 0.8wt.%, 0.9wt.%, 0.85wt.%, 1.0wt.%.
3rd series embodiment
This series embodiment is had altogether including five kinds of compositions, and numbering is 3-1,3-2,3-3,3-4 and 3-5 respectively.Specifically
Composition refers to table 1.
By the ZnO that purity is more than 99.7%, purity is more than 99.99% ZrO2, purity is more than 99.84%
TiO2, purity is more than 99.99% Nb2O5With the CuO that purity is more than 99.5%, by the 3 (y=19- of (x+y)=169
37.66) dispensing is carried out, its TiO2,(Zn1/3Nb2/3)O2,ZrO2Mole percent level and CuO mass percentage content pair
The embodiment numbering 3-1 to 3-5 of table 1 is answered, tableting pressure is 50MPa, and calcined temperature is 1050 DEG C, and burn-in time is 4h, other
Part is same as Example 1.
4th series embodiment
This series embodiment is had altogether including three kinds of compositions, and numbering is 4-1,4-2 and 4-3 respectively.Specific composition can join
Examine table 1.
By the ZnO that purity is more than 99.7%, purity is more than 99.99% ZrO2, purity is more than 99.84%
TiO2, purity is more than 99.99% Nb2O5With the CuO that purity is more than 99.5%, by 123x=-112 (y-60) (y=
Dispensing 6.7-19) is carried out, its TiO2,(Zn1/3Nb2/3)O2,ZrO2Mole percent level and CuO mass percentage content
The embodiment numbering 4-1 to 4-3 of corresponding table 1, tableting pressure is 50MPa, and calcined temperature is 950 DEG C, and burn-in time is 4h, other
Part is same as Example 1.
5th series embodiment
This series embodiment is had altogether including four kinds of compositions, and numbering is 5-1,5-2,5-3 and 5-4 respectively.Specific composition
Refer to table 1.
By the ZnO that purity is more than 99.7%, purity is more than 99.99% ZrO2, purity is more than 99.84%
TiO2, purity is more than 99.99% Nb2O5With the CuO that purity is more than 99.5%, by 15 (x-52)=- 2 (y-14) (y=
Dispensing 14-24) is carried out, its TiO2,(Zn1/3Nb2/3)O2,ZrO2Molar percentage content and the mass percentage content of CuO
The embodiment numbering 5-1 to 5-4 of corresponding table 1, tableting pressure is 50MPa, and calcined temperature is 950 DEG C, and burn-in time is 4h, other
Part is same as Example 1.
6th series embodiment
This series embodiment is had altogether including four kinds of compositions, and numbering is 6-1,6-2,6-3 and 6-4 respectively.Specific composition
Refer to table 1.
By the ZnO that purity is more than 99.7%, purity is more than 99.99% ZrO2, purity is more than 99.84%
TiO2, purity is more than 99.99% Nb2O5With the CuO that purity is more than 99.5%, by 15 (x-52)=- 44 (y-14) (y=
Dispensing 15-19) is carried out, its TiO2,(Zn1/3Nb2/3)O2,ZrO2Mole percent level and CuO mass percentage content pair
The embodiment numbering 6-1 to 6-4 of table 1 is answered, tableting pressure is 50MPa, and calcined temperature is 950 DEG C, and burn-in time is 4h, other portions
Divide same as Example 1.
Measuring in above-described embodiment First Series embodiment to the 6th using Agilent E5701C type Network Analyzers is
The microwave dielectric property of the microwave dielectric ceramic materials of row embodiment, as a result as shown in table 1.
The microwave dielectric property of nearly zero ceramics of the temperature coefficient of resonance frequency of table 1
In above table, the implication of parameters is respectively：X, y, (100-x-y) refer respectively to TiO in ternary system2、
(Zn1/3Nb2/3)O2、ZrO2Mole percent level, unit is mol%；M refers to that doping CuO mass accounts for ZnO, Nb2O5、ZrO2
And TiO2The gross mass degree of powder, unit is wt%；εrIt refer to the relative dielectric constant of sample；Q × f refers to sample
The quality factor of product；τfIt refer to the temperature coefficient of resonance frequency of sample.
As shown in Table 1, under respective optimal sintering temperature, in First Series example, embodiment 1-2,1-3,1-4,1-5
Ceramic dielectric constant εrBetween 37-43.3, temperature coefficient of resonance frequency τfWhole nearly zero, quality factor q × f=19000~
27000GHz。
The ceramic dielectric constant ε of second series embodimentrBetween 37~46.8, temperature coefficient of resonance frequency τfIt is all near
Zero, quality factor q × f=12500~17500GHz.
In 3rd series embodiment, the ceramic dielectric constant ε of embodiment 3-1,3-2,3-3,3-4rIt is humorous between 33~38
Vibration frequency temperature coefficient τfWhole nearly zero, quality factor q × f=18000~24000GHz.
In 4th series embodiment, the ceramic dielectric constant ε of embodiment 4-2,4-3rBetween 40~41, resonant frequency temperature
Degree coefficient τfWhole nearly zero, quality factor q × f=23000GHz.
The ceramic dielectric constant ε of the 5th series embodimentrBetween 40.8~43.6, temperature coefficient of resonance frequency τfAll
Nearly zero, quality factor q × f=16000~21000GHz.
The ceramic dielectric constant ε of the 6th series embodimentrBetween 36.2~40.4, temperature coefficient of resonance frequency τfAll
Nearly zero, quality factor q × f=24000~27000GHz.
Fig. 3 is six kinds of X-ray diffractograms (XRD) of composition ceramics in First Series embodiment of the present invention, as seen from the figure,
From embodiment 1-1 to 1-6, the principal crystalline phase of ceramics sample is from ZrTiO4Structure is mutually gradually varied to ZrTi2O6Structure phase.It is wherein real
Apply in a 1-1 and there is ZrO2The secondary crystalline phase of structure phase.There is TiO in embodiment 1-5 and 1-62The secondary crystalline phase of structure phase.
Fig. 4 is eight kinds of X-ray diffractograms (XRD) of composition ceramics in second series embodiment of the present invention, as seen from the figure,
In embodiment 2-1 to 2-4, principal crystalline phase is ZrTi in ceramics sample2O6Structure phase, secondary crystalline phase is TiO2Structure phase.Embodiment 2-5,
Principal crystalline phase is Zn in ceramics sample0.15Nb0.3Ti0.55O2Structure phase, secondary crystalline phase is ZnTiNb2O8Structure phase.Embodiment 2-6 is in fact
A 2-8 is applied, principal crystalline phase is ZnTiNb in ceramics sample2O8Structure phase, secondary crystalline phase is Zn0.15Nb0.3Ti0.55O2Structure phase.
Fig. 5 is five kinds of X-ray diffractograms (XRD) of composition ceramics in the 3rd series embodiment of the invention, as seen from the figure,
The principal crystalline phase of ceramics sample is ZrTiO4Structure phase, with the increase of y contents, collection of illustrative plates near 34 ° more generates a peak,
According to comparison, illustrate that ceramics sample has gradually to ZrTi2O6The trend of structure phase in version.
Fig. 6 is three kinds of X-ray diffractograms (XRD) of composition ceramics in the 4th series embodiment of the invention, as seen from the figure,
The principal crystalline phase of ceramics sample is ZrTiO4Structure phase, mutually generates without other para-crystals, with the increase of y contents, does not also have near 34 °
There is new peak to generate, illustrate that ceramics sample is purer ZrTiO within this range4Structure phase.
Fig. 7 is four kinds of X-ray diffractograms (XRD) of composition ceramics in the 5th series embodiment of the invention, as seen from the figure,
The principal crystalline phase of ceramics sample is ZrTi2O6Structure phase and occur in that time rutile crystalline phase TiO2Structure phase, it is upper with y contents
Rise, the peak intensity of time crystalline phase gradually rises in collection of illustrative plates, illustrate that the ratio of time crystalline phase in ceramics sample increases with the increase of y.
Fig. 8 is four kinds of X-ray diffractograms (XRD) of composition ceramics in the 6th series embodiment of the invention, as seen from the figure,
The principal crystalline phase of ceramics sample is ZrTi2O6Structure phase, with the increase of y contents, collection of illustrative plates is gradually moved to left at 36 ° of peak, according to than
It is right, find the oriented ZrTiO of sample4The trend of structure phase in version.
Fig. 9 is the scanned photograph figure (SEM figures) that numbering is 1-1 composition ceramics in First Series embodiment of the present invention, by scheming
Understand, there is the region of obvious two kinds of different colours in figure.Wherein darker regions are ZrTiO4Structure phase, light areas are ZrO2
Structure phase.There is obvious crackle without point-like particle between its grain surface and crystal boundary, between crystal grain.
Figure 10 is the scanned photograph figure (SEM figures) that numbering is 1-2 composition ceramics in First Series embodiment of the present invention, by scheming
Understand, a kind of color region is only existed in figure, and it is ZrTiO4Structure phase, has many small between grain surface and crystal boundary
Grain, the little particle on grain surface is most.
Figure 11 is the scanned photograph figure (SEM figures) that numbering is 1-3 composition ceramics in First Series embodiment of the present invention, by scheming
Understand, a kind of color region is only existed in figure, and it is ZrTi2O6Structure phase, has many small between grain surface and crystal boundary
Grain, the little particle on grain surface is less.
Figure 12 is the scanned photograph figure (SEM figures) that numbering is 1-4 composition ceramics in First Series embodiment of the present invention, by scheming
Understand, a kind of color region is only existed in figure, and it is ZrTi2O6Structure phase, has many small between grain surface and crystal boundary
Grain, the little particle on grain surface is less.
Figure 13 is the scanned photograph figure (SEM figures) that numbering is 1-5 composition ceramics in First Series embodiment of the present invention, by scheming
Understand there are apparent dark and light two regions in figure, wherein darker regions are TiO2Structure phase, light areas are
ZrTi2O6Structure phase.
Figure 14 is the scanned photograph figure (SEM figures) that numbering is 1-6 composition ceramics in First Series embodiment of the present invention, by scheming
Understand there are apparent dark and light two regions in figure, wherein darker regions are TiO2Structure phase, light areas are
ZrTi2O6Structure phase.
In the present invention, temperature coefficient of resonance frequency nearly zero refers to -15≤τf≤15ppm/℃。
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (9)
1. a kind of microwave-medium ceramics of temperature coefficient of resonance frequency nearly zero, it is characterised in that the microwave-medium ceramics formula
Composition falls within xTiO2-y(Zn1/3Nb2/3)O2-(100-x-y)ZrO2In the setting compositing area of ternary system,
The setting compositing area refers to that nine line segments are constituted according to sequencing successively head and the tail connection in the ternary system
Closed area,
Nine line segments are nine line segments in the following order,
First line segment：X-y=-7.8, wherein, y=30.99~33.14；
Article 2 line segment：X+y=58.48, wherein, y=21.52~33.14；
Article 3 line segment：X-2.65y=-20.07, wherein, y=21.52~25.73；
Article 4 line segment：2.46x+y=144.1, wherein, y=25.73~69.83；
Article 5 line segment：X+y=100, wherein y=63.52-69.83；
Article 6 line segment：2.45x+y=152.8, wherein, y=23.10~63.52；
Article 7 line segment：7.74x+y=432.39, wherein, y=13.5~23.10；
Article 8 line segment：X-1.525y=33.54, wherein, y=7.86~13.5；
Article 9 line segment：X+0.966y=53.11, wherein, y=7.86~30.99；
Wherein, x, y and (100-x-y) are respectively TiO in ternary system2、(Zn1/3Nb2/3)O2And ZrO2Molar percentage contain
Amount, unit is mol%.
2. the application of the microwave-medium ceramics of a kind of temperature coefficient of resonance frequency as claimed in claim 1 nearly zero.
3. application as claimed in claim 2, it is characterised in that it is used to prepare mobile communication base station dielectric filter, resonance
Device and antenna.
4. a kind of microwave-medium ceramics of temperature coefficient of resonance frequency nearly zero, it is characterised in that the microwave-medium ceramics formula
Composition falls within xTiO2-y(Zn1/3Nb2/3)O2-(100-x-y)ZrO2In the setting composition line segment of ternary system, wherein,
First line segment：3 (x-40)=8 (y-20), wherein, y=16~25；
Article 2 line segment：20 (x-44.17)=- 8.13 (y-20), wherein, y=29.56~66.67；
Article 3 line segment：3 (x+y)=169, wherein, y=19~37.66；
Article 4 line segment：123x=-112 (y-60), wherein, (y=6.7~19)；
Article 5 line segment：15 (x-52)=- 2 (y-14), wherein, (y=14~24)；
Article 6 line segment：15 (x-52)=- 44 (y-14), wherein, (y=15~19)；
Wherein, x, y and (100-x-y) are respectively TiO in ternary system2、(Zn1/3Nb2/3)O2And ZrO2Mole percent level,
Unit is mol%.
5. the application of the microwave-medium ceramics of a kind of temperature coefficient of resonance frequency as claimed in claim 4 nearly zero.
6. application as claimed in claim 5, it is characterised in that it is applied to prepare mobile communication base station dielectric filter, humorous
Shake device and antenna.
7. a kind of method of the microwave-medium ceramics of the temperature coefficient of resonance frequency nearly zero prepared as described in claim 1 and 4, its
It is characterised by,
First, by ZnO, Nb2O5、TiO2、ZrO2And the mixing of CuO powder,
Then, deionized water is added, ball milling obtains uniform mixture,
Then, mixture is dried, in 950 DEG C~1050 DEG C pre-burning 3h~4h,
Again, deionized water is added, secondary ball milling obtains uniform mixture,
Followed by, base substrate will be pressed into after mixture drying, granulation and sieving,
Finally, 3h~4h will be sintered after base substrate dumping at 1260 DEG C~1300 DEG C, obtains temperature coefficient of resonance frequency nearly zero
Ceramic material.
8. method as claimed in claim 7, it is characterised in that the mass percentage content of CuO is ZnO, Nb2O5、ZrO2And
TiO20.5wt.%~the 1.0wt.% of powder gross mass, preferably 0.5wt.%.
9. method as claimed in claim 8, it is characterised in that use powder compressing machine to be suppressed to obtain base substrate, powder
Tablet press machine briquetting pressure is 50MPa~100Mpa.
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Citations (2)
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|---|---|---|---|---|
| US5356843A (en) * | 1992-09-10 | 1994-10-18 | Matsushita Electric Industrial Co., Ltd. | Dielectric ceramic compositions and dielectric resonators |
| CN102503405A (en) * | 2011-11-22 | 2012-06-20 | 电子科技大学 | Compound BZT microwave ceramic dielectric material and preparation method thereof |
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2017
- 2017-02-27 CN CN201710108034.6A patent/CN106854079A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5356843A (en) * | 1992-09-10 | 1994-10-18 | Matsushita Electric Industrial Co., Ltd. | Dielectric ceramic compositions and dielectric resonators |
| CN102503405A (en) * | 2011-11-22 | 2012-06-20 | 电子科技大学 | Compound BZT microwave ceramic dielectric material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| ZHIYUAN CUI ET AL.: "Influence of Zr/Ti Ratio on the Microwave Dielectric Behavior of xZrO2-0.4(Zn1/3Nb2/3)O2-yTiO2 Ceramics", 《JOURNAL OF ELECTRONIC MATERIALS》 * |
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