CN107140981A - A kind of ZnTiNb2O8Series microwave dielectric ceramic material and preparation method thereof - Google Patents
A kind of ZnTiNb2O8Series microwave dielectric ceramic material and preparation method thereof Download PDFInfo
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- CN107140981A CN107140981A CN201710388583.3A CN201710388583A CN107140981A CN 107140981 A CN107140981 A CN 107140981A CN 201710388583 A CN201710388583 A CN 201710388583A CN 107140981 A CN107140981 A CN 107140981A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000006104 solid solution Substances 0.000 abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 abstract description 5
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 16
- 238000005245 sintering Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910019792 NbO4 Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
The invention belongs to electronic ceramics and its manufacture field, and in particular to a kind of ZnTiNb2O8Series microwave dielectric ceramic material and preparation method thereof.The material that the present invention is provided, dielectric constant 30 46, loss≤1.5 × 10‑4, 10ppm/ DEG C of frequency-temperature coefficient≤τf≤+10ppm/ DEG C, principal crystalline phase ZnTiNb2O8, the second phase Zn0.17Nb0.33Ti0.5O2.By raw material ZnO, TiO2, Nb2O5, Co2O3And Ta2O5By chemical general formula (Zn1‑xCox)0.5Ti0.5(Nb1‑yTay)O4(0≤x≤0.95mol, y=0.05 0.95mol) is matched, then is made by solid phase method.The present invention replaces Zn, Nb ion respectively using Co and Ta ions, forms limit solid solution, and temperature coefficient is formd for the second positive phase beyond solid solution part, so as to regulating frequency temperature coefficient nearly 0, and good microwave property is maintained, its preparation method technique is simple, it is easy to industrialized production.
Description
Technical field
The invention belongs to electronic ceramics and its manufacture field, and in particular to a kind of ZnTiNb2O8Series microwave dielectric ceramic material
And preparation method thereof.
Background technology
Microwave-medium ceramics refer to be applied in microwave (300MHz to 300GHz) band circuitry be used as dielectric material and real
The ceramic material of existing one or more function, is the basis in modern communication technology.
The integrated of microwave circuit is to realize miniaturization of microwave equipment, high stability and cheap important means.Due to metal
Resonator and the excessive development for limiting microwave integrated circuit of metal waveguide volume and weight, and microwave-medium ceramics making is humorous
The microwave hybrid integrated circuit for the compositions such as device and microwave tube, microstrip line of shaking, can make device size reach millimeter magnitude, this just makes micro-
Ripple ceramics turn into basis and the critical material for realizing microwave control function.Microwave-medium ceramics are widely used in dielectric resonance
The microwave devices such as device, wave filter, dielectric substrate, Medium Wave Guide loop, microwave capacitors, duplexer, antenna.
Applied to the dielectric ceramic of microwave frequency band, it should meet claimed below：(1) moderate dielectric constant is in favor of device
Miniaturization；(2) high quality factor q × f values and low loss (wherein Q~1/tan δ, f are resonant frequencies)；(3) nearly zero it is humorous
Vibration frequency temperature coefficient.
ZnTiNb2O8Ceramics have good microwave dielectric property, ZnTiNb2O8：εr=34, Q × f=42500GHz, τf
=-72ppm/ DEG C.But its resonant frequency temperature stabilization coefficient fails close to zero, temperature stability is bad to limit its application.
The temperature coefficient of regulation microwave dielectric material, which obtains method, under normal circumstances has：Introduce the opposite material of temperature coefficient or carry out from
Son substitution.But in ZnTiNb2O8It is middle add temperature coefficient be on the occasion of material such as TiO2, but can not densified sintering product, cause microwave to be situated between
Electrical property declines.Therefore on the premise of material performance parameter itself is ensured, resonant frequency temperature stabilization system how is effectively solved
Number turns into a problem.
The content of the invention
The goal of the invention of the present invention is intended to improvement resonant frequency temperature stability, and there is provided a kind of ZnTiNb2O8It is that microwave is situated between
Ceramics and preparation method thereof.
The ZnTiNb that the present invention is provided2O8Series microwave dielectric ceramic material, with Medium dielectric constant (30-46), low-loss
(≤1.5×10-4), (- 10ppm/ DEG C≤τ of frequency-temperature coefficient nearly zerof≤+10ppm/ DEG C), principal crystalline phase is ZnTiNb2O8, second
It is mutually Zn0.17Nb0.33Ti0.5O2。
Its raw material composition is ZnO, TiO2, Nb2O5, Co2O3And Ta2O5, by chemical general formula (Zn1-xCox)0.5Ti0.5(Nb1- yTay)O4Match (0≤x≤0.95mol, y=0.05-0.95mol), be made by solid phase method.
Its preparation method is specific as follows：
Step 1：By ZnO, Co2O3、TiO2、Nb2O5、Ta2O5Starting powder according to chemical general formula (Zn1-xCox)0.5Ti0.5
(Nb1-yTay)O4(0≤x≤0.95mol, y=0.05-0.95mol) dispensing.
Step 2：By step 1 gained dispensing：Zirconia ball：Deionized water, with mass ratio 1:3-7:1-3 is matched, planet ball
Mill 4-8 hours, is then dried at 80 DEG C -120 DEG C, then is sieved with 40-60 eye mesh screens, finally in 800 DEG C of -1000 DEG C of atmospheres
Enclose middle pre-burning 2-6 hours synthesis principal crystalline phase ZnTiNb2O8；
Step 3：By step 2 gained powder according to powder：Zirconia ball：Deionized water quality compares 1:3-7:1-3, planet ball
Mill mixing 4-8 hours, is then dried, additive capacity accounts for 2~5% PVA solution of its quality after drying at 80 DEG C -100 DEG C
Granulated as binding agent, it is compressing, finally sintered 4-6 hours in 1150 DEG C of -1200 DEG C of air atmospheres, ZnTiNb is made2O8
Series microwave dielectric ceramic material is micro-.
The present invention replaces Zn, Nb ion respectively using Co and Ta ions, forms limit solid solution, is formed beyond solid solution part
Temperature coefficient is the second positive phase, thus regulating frequency temperature coefficient nearly 0, and good microwave property is maintained, it is prepared
Method technique is simple, it is easy to industrialized production.
Brief description of the drawings
Fig. 1 (1) is embodiment 7.19.31 XRD, and Fig. 1 (2) is embodiment 17.18.19.20 XRD；
Fig. 2 (1) is embodiment 7.19.31 surface topography map, and Fig. 2 (2) is embodiment 17.18.19.20 surface topography
Figure.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Step 1, by ZnO, Co2O3、TiO2、Nb2O5And Ta2O5Starting powder according to chemical general formula (Zn1-xCox)0.5Ti0.5
(Nb1-yTay)O4(0≤x≤0.3mol, y=0.2-0.4mol) dispensing.
Step 2, by step 1 gained powder, according to powder：Zirconia ball：The mass ratio 1 of deionized water:5:2 add nylon
In tank, planetary ball mill mix 6 hours, after taking-up at 100 DEG C dry, with 60 eye mesh screens sieve, after in 1000 DEG C of atmospheric atmospheres
3 hours synthesis principal crystalline phase ZnTiNb of middle pre-burning2O8。
Step 3, by after step 2 pre-burning gained powder according to powder：Zirconia ball：The mass ratio 1 of deionized water:5:1
Add in nylon tank, planetary ball mill is mixed 4 hours, dried after taking-up at 100 DEG C, additive capacity accounts for its quality after drying
4% PVA solution is granulated as binding agent, compressing, is finally sintered 6 hours in 1175 DEG C of air atmospheres, microwave is made
Medium ceramic material.
Fig. 1 (1) be embodiment 7.19.31 XRD, 1175 DEG C of sintering temperature, during x=0.2, different y values (Ta contents)
Influence to Sample crystals structure.In the case of three groups of difference Ta contents, principal crystalline phase and ZnTiNb2O8Card (JCPDS#48-
0323) match, while under each Ta contents, sample has the second phase Zn0.17Nb0.33Ti0.5O2(JCPDS#39-0291), and
With the increase of Ta contents, the enhancing of the second phase peak intensity corresponds to the increase of its content.
Fig. 1 (2) be embodiment 17.18.19.20 XRD, 1175 DEG C of sintering temperature, during y=0.3, (Co contains different x values
Amount) influence to Sample crystals structure.In the case of four groups of difference Co contents, principal crystalline phase peak and ZnTiNb2O8Matching, when Co contains
When amount is more than 0.2, there is the second phase Zn0.17Nb0.33Ti0.5O2, and during Co content increases, the enhancing of the second phase peak intensity.
Fig. 2 (1) is sample (Zn1-xCox)0.5Ti0.5(Nb1-yTay)O4The surface of (x=0.2mol, y=0.2-0.4mol)
Shape appearance figure, main to inquire into 1175 DEG C, during x=0.2, different y values (Ta contents) influence on the pattern of sample.Wherein (a) correspondence is real
Apply example 7, (b) correspondence embodiment 19, (c) correspondence embodiment 31. are it can be seen that as y=0.2, sample surfaces stomata
It is more, and there is hole of holding one's breath, grain size is uneven, in the majority with big crystal grain；As y=0.3, grain development, hence it is evident that find out and close
Stomata is disappeared, and surface pores is reduced, now still with the presence of the uneven crystal grain of size；During y=0.4, sample surfaces are more caused
It is close, there is abnormal big crystal grain, crystal grain non-uniform phenomenon is still suffered from, but compared with for (a), big crystal grain quantity is reduced, little crystal grain quantity
Increase.
Fig. 2 (2) is sample (Zn1-xCox)0.5Ti0.5(Nb1-yTay)O4The surface shape of (0≤x≤0.3mol, y=0.3mol)
Looks figure, main to inquire into 1175 DEG C, during y=0.3, different x values (Co contents) influence on the pattern of sample.Wherein (a) correspondence is implemented
Example 17, (b) correspondence embodiment 18, (c) correspondence embodiment 19, (d) correspondence embodiment 20.It can be seen that in any Co
Under volume, the surface pores of sample is less, and sample consistency is high under the conditions of illustrating this, occurs the presence of bar-shaped crystalline substance in figure (a)
And the uneven crystal grain of size, little crystal grain is in the majority, and big crystal grain is excessive, it may be possible to which misgrowth is caused；And in figure (b), it is bright
Aobvious to can't see bar-shaped brilliant presence, crystal grain is mainly in the majority with big crystal grain, with the presence of a small amount of little crystal grain；In figure (c), there is size
Crystal grain, little crystal grain quantity is more, and Co too high levels cause abnormal grain occur in figure (d).
The composition and microwave dielectric property of embodiment are as follows
As can be seen from the above table, Co2O3And Ta2O5Addition can suitably lift dielectric constant, keep relatively low loss,
Resonant frequency temperature stabilization coefficient is improved, and adulterate Ta, Co mole for 0.3 and 0.2 when and undoped with Ta, Co
Zn0.5Ti0.5NbO4Contrast (embodiment 15,19,23), temperature stability is more excellent.
As fully visible, the present invention replaces Zn, Nb ion respectively using Co and Ta ions, forms limit solid solution, beyond solid
Molten part forms temperature coefficient for the second positive phase, so that regulating frequency temperature coefficient nearly 0, and maintain good microwave
Can, its preparation method, technique is simple, it is easy to industrialized production.
Claims (2)
1. a kind of ZnTiNb2O8Series microwave dielectric ceramic material, it is characterised in that：
Principal crystalline phase is ZnTiNb2O8, second is mutually Zn0.17Nb0.33Ti0.5O2, dielectric constant 30-46, loss≤1.5 × 10-4, frequency
- 10ppm/ DEG C of rate temperature coefficient≤τf≤+10ppm/℃；
Its raw material composition is ZnO, TiO2, Nb2O5, Co2O3And Ta2O5, by chemical general formula (Zn1-xCox)0.5Ti0.5(Nb1-yTay)O4
Proportioning, 0≤x≤0.95mol, 0.05≤y≤0.95mol are made by solid phase method.
2. ZnTiNb as claimed in claim 12O8The preparation method of series microwave dielectric ceramic material, it is specific as follows：
Step 1：ZnO、Co2O3、TiO2、Nb2O5And Ta2O5Starting powder according to chemical general formula (Zn1-xCox)0.5Ti0.5(Nb1- yTay)O4Dispensing, 0≤x≤0.95mol, 0.05≤y≤0.95mol；
Step 2：By step 1 gained dispensing：Zirconia ball：Deionized water, with mass ratio 1:3-7:1-3 is matched, planetary ball mill 4-8
Hour, then dried at 80 DEG C -120 DEG C, then sieved with 40-60 eye mesh screens, finally in 800 DEG C of -1000 DEG C of atmospheric atmospheres
2-6 hours synthesis principal crystalline phase ZnTiNb of pre-burning2O8；
Step 3：By step 2 gained powder according to powder：Zirconia ball：Deionized water, with mass ratio 1:3-7:1-3, planet ball
Mill mixing 4-8 hours, is then dried, additive capacity accounts for 2~5% PVA solution of its quality after drying at 80 DEG C -100 DEG C
Granulated as binding agent, it is compressing, finally sintered 4-6 hours in 1150 DEG C of -1200 DEG C of air atmospheres, ZnTiNb is made2O8
Series microwave dielectric ceramic material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721421A (en) * | 2017-10-30 | 2018-02-23 | 电子科技大学 | A kind of Zn Nb Ti systems LTCC materials and preparation method thereof |
| CN109251029A (en) * | 2018-11-15 | 2019-01-22 | 西华大学 | A kind of temperature-stabilized microwave medium ceramic material and preparation method thereof |
| CN109467432A (en) * | 2018-12-14 | 2019-03-15 | 电子科技大学 | A kind of Mg-Ti-Ta base microwave medium ceramic material and preparation method thereof |
| CN109503162A (en) * | 2018-12-14 | 2019-03-22 | 电子科技大学 | A kind of Co-Sn-Ta base microwave medium ceramic material and preparation method thereof |
| CN109574663A (en) * | 2018-12-14 | 2019-04-05 | 电子科技大学 | A kind of Ni-Ti-Ta base microwave medium ceramic material and preparation method thereof |
| CN110137493A (en) * | 2019-06-02 | 2019-08-16 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of a kind of oxygen defect zinc niobate negative electrode material and application |
| US11390564B2 (en) * | 2018-12-14 | 2022-07-19 | University Of Electronic Science And Technology Of China | Ceramic material and method for preparing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005008468A (en) * | 2003-06-18 | 2005-01-13 | Ube Ind Ltd | Dielectric ceramic composition and laminated ceramic component using the same |
| CN101462874A (en) * | 2008-11-28 | 2009-06-24 | 西安交通大学 | Low temperature sintering middle-dielectric constant microwave-medium ceramic material and preparation method thereof |
| CN102617144A (en) * | 2012-04-05 | 2012-08-01 | 天津大学 | Novel temperature stable type tantalum niobate microwave dielectric ceramic |
| CN102815944A (en) * | 2012-08-27 | 2012-12-12 | 天津大学 | Cobalt doped niobium zinc titanate microwave dielectric ceramics and preparation method thereof |
| CN103058657A (en) * | 2013-01-17 | 2013-04-24 | 天津大学 | Microwave dielectric ceramics doped with cobalt oxide and niobium zinc titanate |
-
2017
- 2017-05-27 CN CN201710388583.3A patent/CN107140981B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005008468A (en) * | 2003-06-18 | 2005-01-13 | Ube Ind Ltd | Dielectric ceramic composition and laminated ceramic component using the same |
| CN101462874A (en) * | 2008-11-28 | 2009-06-24 | 西安交通大学 | Low temperature sintering middle-dielectric constant microwave-medium ceramic material and preparation method thereof |
| CN102617144A (en) * | 2012-04-05 | 2012-08-01 | 天津大学 | Novel temperature stable type tantalum niobate microwave dielectric ceramic |
| CN102815944A (en) * | 2012-08-27 | 2012-12-12 | 天津大学 | Cobalt doped niobium zinc titanate microwave dielectric ceramics and preparation method thereof |
| CN103058657A (en) * | 2013-01-17 | 2013-04-24 | 天津大学 | Microwave dielectric ceramics doped with cobalt oxide and niobium zinc titanate |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721421A (en) * | 2017-10-30 | 2018-02-23 | 电子科技大学 | A kind of Zn Nb Ti systems LTCC materials and preparation method thereof |
| CN107721421B (en) * | 2017-10-30 | 2020-09-25 | 电子科技大学 | Zn-Nb-Ti LTCC material and preparation method thereof |
| CN109251029A (en) * | 2018-11-15 | 2019-01-22 | 西华大学 | A kind of temperature-stabilized microwave medium ceramic material and preparation method thereof |
| CN109251029B (en) * | 2018-11-15 | 2019-07-02 | 西华大学 | A kind of temperature-stabilized microwave medium ceramic material and preparation method thereof |
| CN109467432A (en) * | 2018-12-14 | 2019-03-15 | 电子科技大学 | A kind of Mg-Ti-Ta base microwave medium ceramic material and preparation method thereof |
| CN109503162A (en) * | 2018-12-14 | 2019-03-22 | 电子科技大学 | A kind of Co-Sn-Ta base microwave medium ceramic material and preparation method thereof |
| CN109574663A (en) * | 2018-12-14 | 2019-04-05 | 电子科技大学 | A kind of Ni-Ti-Ta base microwave medium ceramic material and preparation method thereof |
| CN109467432B (en) * | 2018-12-14 | 2021-03-30 | 电子科技大学 | Mg-Ti-Ta-based microwave dielectric ceramic material and preparation method thereof |
| CN109503162B (en) * | 2018-12-14 | 2021-05-04 | 电子科技大学 | Co-Sn-Ta-based microwave dielectric ceramic material and preparation method thereof |
| US11390564B2 (en) * | 2018-12-14 | 2022-07-19 | University Of Electronic Science And Technology Of China | Ceramic material and method for preparing the same |
| CN110137493A (en) * | 2019-06-02 | 2019-08-16 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of a kind of oxygen defect zinc niobate negative electrode material and application |
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