两种Ti基微波介质陶瓷的制备与性能研究
发布时间：2018-08-30 13:33
【摘要】：微波介质陶瓷材料是一种近30年来快速发展的新型电子功能陶瓷材料，它被广泛应用于300MHz~3000GHz的微波频段。微波介质陶瓷具有高介电常数(ε_r)、低介电损耗(tan δ，或者高Q×f， Q=1/tanδ)和小谐振频率温度系数(τ_f)，常以介质谐振器的形式出现在微波振荡器、滤波器、天线等微波器件中；其次在LTCC技术中，900℃左右低温烧成的微波介质陶瓷还可作为微波电路中的介质基板材料。近年来，微波介质陶瓷材料需求持续旺盛，研制拥有自主知识产权的新型微波介质陶瓷，已经成为战略性、前沿性和前瞻性高技术问题。本文采用固相法合成陶瓷粉体，以及传统陶瓷工艺制备陶瓷样品，面向实际应用，从材料组份对陶瓷物相组成、微观结构和微波介电性能影响出发，围绕BaTi_4O_9-BaZn_2Ti_4O_(11)和ZrTi_2O_6-ZnNb_2O_6两种Ti基微波介质陶瓷展开，得到了如下的主要研究成果： 1.通过一次固相合成工艺，制备出了能够相互稳定共生且共存的(1-x)BaTi_4O_(9-x)BaZn_2Ti_4O_(11)复相微波介质陶瓷。当x从0.05增加到0.50，BaZn_2Ti_4O_(11)晶相的相对含量能稳定增加，陶瓷介电常数从ε_r=37.3减小到ε_r=32.8； Q×f值先从45300GHz增加到峰值60600GHz(x=0.30)，然后下降到58700GHz(x=0.40)；频率温度系数从τ_f=+12ppm/℃以近似直线的趋势下降到τ_f=-3ppm/℃。最终，0.7BaTi_4O_9-0.3BaZn_2Ti_4O_(11)复相介质陶瓷在1240℃烧结3h致密，微波介电性能最优为：ε_r=34.2， Q×f=60600GHz，τ_f=-2.0ppm/℃。 2.通过掺杂CuO形成液相烧结，将BaTi_4O_9-BaZn_2Ti_4O_(11)复相微波介质陶瓷烧结温度降到1150℃。此外，Cu~(2+)可对Zn~(2+)进行取代，使BaZn_2Ti_4O_(11)晶相的相对含量提高，而且还降低了其晶格常数，这都有益于陶瓷Q×f值的提高；而且，发现进行适量Cu~(2+)离子取代可以抑制BaZn_(2-x)Cu_xTi_4O_(11)微波介质陶瓷在空气中烧结时发生的失氧反应，使Q×f值的稳定性和重复性提高了。掺杂1.0wt%CuO的0.85BaTi_4O_9-0.15BaZn_2Ti_4O_(11)复相介质陶瓷在1150℃保温3h就能获得致密的微观结构，而且微波介电性能更加优异：ε_r=36.4， Q×f=62600GHz，τ_f=+0.2ppm/℃，综合微波介电性能优于许多公开报道的同类微波介质陶瓷，具有实际应用潜力。在10Kg扩大试验中，此微波介质陶瓷的性能优异且稳定，，经相关厂家验证此新型微波介质具有商业化应用潜力。 3.为了满足LTCC技术要求，通过掺杂低温烧结助剂BaCu(B_2O_5)，使BaTi_4O_9-BaZn_2Ti_4O_(11)微波介质陶瓷烧结温度降低至900℃。掺杂BaCu(B_2O_5)会导致部分BaTi_4O_9相分解为Ba4Ti13O30，以及新杂相BaTi(BO3)2生成。BaCu(B_2O_5)掺杂也能形成液相烧结机制，并在900℃烧结可以获得相对致密的微观结构。掺杂11wt%BaCu(B_2O_5)并在900℃烧结2h获得的0.85BaTi_4O_9-0.15BaZn_2Ti_4O_(11)介质陶瓷有较好的微波介电性能：ε_r=30.9， Q×f=20200GHz，τ_f=+11.7ppm/℃。此微波介电性能相较于其他BaO-ZnO-TiO_2三元基低烧微波介质陶瓷具有优势，特别是Q×f值相对较高。 4.纯ZrTi_2O_6-ZnNb_2O_6微波介质陶瓷在空气中烧结，会有失氧化学反应，致使其Q×f值非常低。通过掺杂变价元素Mn离子取代Ti~(4+)，会导致原料中TiO2相被遗留下来，构成第二杂相；还能促进晶粒生长。受益于Mn离子的受主作用，掺杂0.7wt%MnCO3的样品在空气中烧结具有最大Q×f=44800GHz，高出在空气中烧结的纯样品的Q×f值15倍以上。最终，掺杂0.7wt%MnCO3的0.69ZrTi_2O_6-0.31ZnNb2O6介质陶瓷可在1270℃的空气中烧结7h致密，且具有良好的微波介电性能：ε_r=45.3， Q×f=43300GHz，τ_f=-0.5ppm/℃。 5.研究了Zr(Zn_(1/3)Nb_(2/3))_xTi_(2-x)O_6(0.2≤x≤0.8)固溶体微波介质陶瓷的晶相组成、微观结构和微波介电性能。复合离子(Zn_(1/3)Nb_(2/3))~(4+)可全部固溶进入Zr-Ti晶相，当x=0.5~0.8时，形成纯ZrTi_2O_6固溶体单相区。在此单相区，随着x值增加，陶瓷样品的介电常数从ε_r=43.0连续下降到ε_r=39.2，τ_f值从τ_f=-10.2ppm/℃减小到τ_f=-25.5ppm/℃， Q×f值从40900GHz增加到43200GHz。 Q×f值增加是由于复合离子(Zn_(1/3)Nb_(2/3))~(4+)对Ti~(4+)离子取代增强了ZrTi_2O_6晶相中的共价键作用。最后，Zr(Zn_(1/3)Nb_(2/3))_(0.6)Ti_(1.4)O_6+0.3wt%MnCO_3陶瓷在1260℃空气中烧结6h，可获得致密的微观结构，为纯Zr(Zn_(1/3)Nb_(2/3))_xTi_(2-x)O_6固溶体单晶相，而且具有好的微波介电性能：ε_r=41.7， Q×f=42100GHz，τ_f=-15.5ppm/℃。
[Abstract]:Microwave dielectric ceramics is a new type of electronic functional ceramics developed rapidly in the past 30 years. It is widely used in the microwave frequency range of 300 MHz to 3000 GHz. Microwave dielectric ceramics have high dielectric constant (e_r), low dielectric loss (tan_ delta, or high Q *f, Q=1/tan_ delta) and small resonant frequency temperature coefficient (__f), often in the form of dielectric resonators. Microwave dielectric ceramics can also be used as dielectric substrate materials in microwave circuits in LTCC technology. In recent years, the demand for microwave dielectric ceramics continues to flourish, and new microwave dielectric ceramics with independent intellectual property rights have been developed. In this paper, ceramic powders were synthesized by solid-state method and ceramic samples were prepared by traditional ceramic process. For practical application, the effects of material composition on phase composition, microstructure and microwave dielectric properties of ceramics were studied, focusing on BaTi_4O_9-BaZn_2Ti_4O_ (11) and ZrTi_2O_6-ZnNb_2O_6. I based microwave dielectric ceramics have been developed and the following main results have been obtained:
1. The (1-x) BaTi_4O_ (9-x) BaZn_2Ti_4O_ (11) multiphase microwave dielectric ceramics which can coexist stably with each other were prepared by One-step Solid-state synthesis. When x increases from 0.05 to 0.50, the relative content of BaZn_2Ti_4O_ (11) phase increases steadily, and the dielectric constant of the ceramics decreases from 37.3 to 32.8, and the Q *f value increases from 45300z at first. The frequency temperature coefficient decreases from96_f = + 12ppm / / 96_f = + 12ppm / to96_f = - 3 ppm / / = - 3 ppm /. Finally, 0.7 BaTi_4O_4O_9 - 0.3 BaZn2BaZn2Ti_2TiO_4O_ (11) composite cerceramics sinterat 240 for 3 h, and the microwave diedielectric properties are optimized as follows: the diediediediediediediediediediediediedielectric properties are optimized as follows: e_r_r = 34.2, Q R = 34.2, Q/ C.
2. By doping CuO to form liquid phase sintering, the sintering temperature of BaTi_4O_9-BaZn_2Ti_4O_ (11) multiphase microwave dielectric ceramics was reduced to 1150 C. In addition, Cu ~ (2+) could replace Zn (2+), and the relative content of BaZn_2Ti_4O_ (11) phase was increased, and the lattice constant was decreased, which was beneficial to the increase of Q F value of ceramics. Cu~ (2+) substitution can inhibit the deoxidization reaction of BaZn_ (2-x) Cu_xTi_4O_ (11) microwave dielectric ceramics sintered in air, which improves the stability and repeatability of Q f value. The 0.85 BaTi_4O_9-0.15 BaZn_2Ti_4O_ (11) multiphase dielectric ceramics doped with 1.0wt% CuO can obtain compact microstructure at 1150 for 3 h, and the microwave dielectric ceramics can obtain compact microstructure. The dielectric properties of the new type of microwave dielectric ceramics are better than those of other similar microwave dielectric ceramics reported in the public. The properties of the new type of microwave dielectric ceramics are excellent and stable in the 10Kg extended test. The new type of microwave dielectric ceramics has been proved to be commercialized by relevant manufacturers. Use potential.
3. In order to meet the technical requirements of LTCC, the sintering temperature of BaTi_4O_9-BaZn_2Ti_4O_ (11) microwave dielectric ceramics was reduced to 900 C by doping low-temperature sintering additive BaCu (B_2O_5). Doping BaCu (B_2O_5) could cause the partial decomposition of BaTi_4O_9 phase into Ba4Ti_13O_ 30 and the formation of new heterogenous BaTi (BO_3) _2. BaCu (B_2O_5) doping could also form liquid-phase sintering mechanism, and the liquid-phase sintering mechanism was also A relatively compact microstructure can be obtained by sintering at 900 C. The 0.85 BaTi_4O_9-0.15 BaZn_2Ti_4O_ (11) dielectric ceramics doped with 11wt% BaCu (B_2O_5) and sintered at 900 C for 2 h have better microwave dielectric properties than other BaO-ZnO-TiO_2 ternary ceramics: e_r=30.9, Q*f=20200GHz, __f=+11.7ppm/ C. Dielectric ceramics have advantages, especially the Q * f value is relatively high.
4. Pure ZrTi_2O_6-ZnNb_2O_6 microwave dielectric ceramics sintered in air will lose oxidation chemical reaction, resulting in very low Q 65507 The sample sintered in air has the maximum Q f = 44800GHz, which is 15 times higher than that of pure sample sintered in air. Finally, 0.69ZrTi_2O_6-0.31ZnNb2O6 dielectric ceramics doped with 0.7wt% MnCO_3 can be sintered in air at 1270 for 7h and have good microwave dielectric properties: e_r = 45.3, Q f = 43300GHz, __f = - 0.5ppm / C.
5. The phase composition, microstructure and microwave dielectric properties of Zr (Zn_ (1/3) Nb_ (2/3) _xTi_ (2-x) O_6 (0.2 < x < 0.8) solid solution microwave dielectric ceramics were studied. Complex ions (Zn_ (1/3) Nb_ (2/3)) ~ (4+) can be all solid solution into Zr-Ti crystalline phase. When x = 0.5 ~ 0.8, pure ZrTi_2O_6 solid solution is formed in this single phase region. The dielectric constant of the product decreases continuously from E_r=43.0 to E_r=43.0 to E_r=39.2, 96_f value decreases fromu_f=-10.2 ppm/ / / to96_f=-25.5 ppm /, Q F value increases from 40900GHz to 43200 GHz.Q. Q (1/3) Nb_ (2 / 3) (2 / 3) ~ (4 +) ~ (4 +) substitutionfor Ti ~ u (1/3) Nb_ (2/3)) _ (0.6) Ti_ (1.4) O_6 + 0.3wt% MnCO_3 ceramics were sintered in air at 1260 C for 6 h, and obtained dense microstructure, which is pure Zr (Zn_ (1/3) Nb_ (2/3))_xTi_ (2-x) O_6 solid solution, and has good microwave dielectric properties: e_r = 41.7, Q f = 100GHz, __f = - 15.5ppm /.
【学位授予单位】：电子科技大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：TM28
本文编号：2213226
[Abstract]:Microwave dielectric ceramics is a new type of electronic functional ceramics developed rapidly in the past 30 years. It is widely used in the microwave frequency range of 300 MHz to 3000 GHz. Microwave dielectric ceramics have high dielectric constant (e_r), low dielectric loss (tan_ delta, or high Q *f, Q=1/tan_ delta) and small resonant frequency temperature coefficient (__f), often in the form of dielectric resonators. Microwave dielectric ceramics can also be used as dielectric substrate materials in microwave circuits in LTCC technology. In recent years, the demand for microwave dielectric ceramics continues to flourish, and new microwave dielectric ceramics with independent intellectual property rights have been developed. In this paper, ceramic powders were synthesized by solid-state method and ceramic samples were prepared by traditional ceramic process. For practical application, the effects of material composition on phase composition, microstructure and microwave dielectric properties of ceramics were studied, focusing on BaTi_4O_9-BaZn_2Ti_4O_ (11) and ZrTi_2O_6-ZnNb_2O_6. I based microwave dielectric ceramics have been developed and the following main results have been obtained:
1. The (1-x) BaTi_4O_ (9-x) BaZn_2Ti_4O_ (11) multiphase microwave dielectric ceramics which can coexist stably with each other were prepared by One-step Solid-state synthesis. When x increases from 0.05 to 0.50, the relative content of BaZn_2Ti_4O_ (11) phase increases steadily, and the dielectric constant of the ceramics decreases from 37.3 to 32.8, and the Q *f value increases from 45300z at first. The frequency temperature coefficient decreases from96_f = + 12ppm / / 96_f = + 12ppm / to96_f = - 3 ppm / / = - 3 ppm /. Finally, 0.7 BaTi_4O_4O_9 - 0.3 BaZn2BaZn2Ti_2TiO_4O_ (11) composite cerceramics sinterat 240 for 3 h, and the microwave diedielectric properties are optimized as follows: the diediediediediediediediediediediediedielectric properties are optimized as follows: e_r_r = 34.2, Q R = 34.2, Q/ C.
2. By doping CuO to form liquid phase sintering, the sintering temperature of BaTi_4O_9-BaZn_2Ti_4O_ (11) multiphase microwave dielectric ceramics was reduced to 1150 C. In addition, Cu ~ (2+) could replace Zn (2+), and the relative content of BaZn_2Ti_4O_ (11) phase was increased, and the lattice constant was decreased, which was beneficial to the increase of Q F value of ceramics. Cu~ (2+) substitution can inhibit the deoxidization reaction of BaZn_ (2-x) Cu_xTi_4O_ (11) microwave dielectric ceramics sintered in air, which improves the stability and repeatability of Q f value. The 0.85 BaTi_4O_9-0.15 BaZn_2Ti_4O_ (11) multiphase dielectric ceramics doped with 1.0wt% CuO can obtain compact microstructure at 1150 for 3 h, and the microwave dielectric ceramics can obtain compact microstructure. The dielectric properties of the new type of microwave dielectric ceramics are better than those of other similar microwave dielectric ceramics reported in the public. The properties of the new type of microwave dielectric ceramics are excellent and stable in the 10Kg extended test. The new type of microwave dielectric ceramics has been proved to be commercialized by relevant manufacturers. Use potential.
3. In order to meet the technical requirements of LTCC, the sintering temperature of BaTi_4O_9-BaZn_2Ti_4O_ (11) microwave dielectric ceramics was reduced to 900 C by doping low-temperature sintering additive BaCu (B_2O_5). Doping BaCu (B_2O_5) could cause the partial decomposition of BaTi_4O_9 phase into Ba4Ti_13O_ 30 and the formation of new heterogenous BaTi (BO_3) _2. BaCu (B_2O_5) doping could also form liquid-phase sintering mechanism, and the liquid-phase sintering mechanism was also A relatively compact microstructure can be obtained by sintering at 900 C. The 0.85 BaTi_4O_9-0.15 BaZn_2Ti_4O_ (11) dielectric ceramics doped with 11wt% BaCu (B_2O_5) and sintered at 900 C for 2 h have better microwave dielectric properties than other BaO-ZnO-TiO_2 ternary ceramics: e_r=30.9, Q*f=20200GHz, __f=+11.7ppm/ C. Dielectric ceramics have advantages, especially the Q * f value is relatively high.
4. Pure ZrTi_2O_6-ZnNb_2O_6 microwave dielectric ceramics sintered in air will lose oxidation chemical reaction, resulting in very low Q 65507 The sample sintered in air has the maximum Q f = 44800GHz, which is 15 times higher than that of pure sample sintered in air. Finally, 0.69ZrTi_2O_6-0.31ZnNb2O6 dielectric ceramics doped with 0.7wt% MnCO_3 can be sintered in air at 1270 for 7h and have good microwave dielectric properties: e_r = 45.3, Q f = 43300GHz, __f = - 0.5ppm / C.
5. The phase composition, microstructure and microwave dielectric properties of Zr (Zn_ (1/3) Nb_ (2/3) _xTi_ (2-x) O_6 (0.2 < x < 0.8) solid solution microwave dielectric ceramics were studied. Complex ions (Zn_ (1/3) Nb_ (2/3)) ~ (4+) can be all solid solution into Zr-Ti crystalline phase. When x = 0.5 ~ 0.8, pure ZrTi_2O_6 solid solution is formed in this single phase region. The dielectric constant of the product decreases continuously from E_r=43.0 to E_r=43.0 to E_r=39.2, 96_f value decreases fromu_f=-10.2 ppm/ / / to96_f=-25.5 ppm /, Q F value increases from 40900GHz to 43200 GHz.Q. Q (1/3) Nb_ (2 / 3) (2 / 3) ~ (4 +) ~ (4 +) substitutionfor Ti ~ u (1/3) Nb_ (2/3)) _ (0.6) Ti_ (1.4) O_6 + 0.3wt% MnCO_3 ceramics were sintered in air at 1260 C for 6 h, and obtained dense microstructure, which is pure Zr (Zn_ (1/3) Nb_ (2/3))_xTi_ (2-x) O_6 solid solution, and has good microwave dielectric properties: e_r = 41.7, Q f = 100GHz, __f = - 15.5ppm /.
【学位授予单位】：电子科技大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：TM28
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