兩種Ti基微波介質(zhì)陶瓷的制備與性能研究
發(fā)布時間：2018-08-30 13:33
【摘要】：微波介質(zhì)陶瓷材料是一種近30年來快速發(fā)展的新型電子功能陶瓷材料，它被廣泛應用于300MHz~3000GHz的微波頻段。微波介質(zhì)陶瓷具有高介電常數(shù)(ε_r)、低介電損耗(tan δ，或者高Q×f， Q=1/tanδ)和小諧振頻率溫度系數(shù)(τ_f)，常以介質(zhì)諧振器的形式出現(xiàn)在微波振蕩器、濾波器、天線等微波器件中；其次在LTCC技術(shù)中，900℃左右低溫燒成的微波介質(zhì)陶瓷還可作為微波電路中的介質(zhì)基板材料。近年來，微波介質(zhì)陶瓷材料需求持續(xù)旺盛，研制擁有自主知識產(chǎn)權(quán)的新型微波介質(zhì)陶瓷，已經(jīng)成為戰(zhàn)略性、前沿性和前瞻性高技術(shù)問題。本文采用固相法合成陶瓷粉體，以及傳統(tǒng)陶瓷工藝制備陶瓷樣品，面向?qū)嶋H應用，從材料組份對陶瓷物相組成、微觀結(jié)構(gòu)和微波介電性能影響出發(fā)，圍繞BaTi_4O_9-BaZn_2Ti_4O_(11)和ZrTi_2O_6-ZnNb_2O_6兩種Ti基微波介質(zhì)陶瓷展開，得到了如下的主要研究成果： 1.通過一次固相合成工藝，制備出了能夠相互穩(wěn)定共生且共存的(1-x)BaTi_4O_(9-x)BaZn_2Ti_4O_(11)復相微波介質(zhì)陶瓷。當x從0.05增加到0.50，BaZn_2Ti_4O_(11)晶相的相對含量能穩(wěn)定增加，陶瓷介電常數(shù)從ε_r=37.3減小到ε_r=32.8； Q×f值先從45300GHz增加到峰值60600GHz(x=0.30)，然后下降到58700GHz(x=0.40)；頻率溫度系數(shù)從τ_f=+12ppm/℃以近似直線的趨勢下降到τ_f=-3ppm/℃。最終，0.7BaTi_4O_9-0.3BaZn_2Ti_4O_(11)復相介質(zhì)陶瓷在1240℃燒結(jié)3h致密，微波介電性能最優(yōu)為：ε_r=34.2， Q×f=60600GHz，τ_f=-2.0ppm/℃。 2.通過摻雜CuO形成液相燒結(jié)，將BaTi_4O_9-BaZn_2Ti_4O_(11)復相微波介質(zhì)陶瓷燒結(jié)溫度降到1150℃。此外，Cu~(2+)可對Zn~(2+)進行取代，使BaZn_2Ti_4O_(11)晶相的相對含量提高，而且還降低了其晶格常數(shù)，這都有益于陶瓷Q×f值的提高；而且，發(fā)現(xiàn)進行適量Cu~(2+)離子取代可以抑制BaZn_(2-x)Cu_xTi_4O_(11)微波介質(zhì)陶瓷在空氣中燒結(jié)時發(fā)生的失氧反應，使Q×f值的穩(wěn)定性和重復性提高了。摻雜1.0wt%CuO的0.85BaTi_4O_9-0.15BaZn_2Ti_4O_(11)復相介質(zhì)陶瓷在1150℃保溫3h就能獲得致密的微觀結(jié)構(gòu)，而且微波介電性能更加優(yōu)異：ε_r=36.4， Q×f=62600GHz，τ_f=+0.2ppm/℃，綜合微波介電性能優(yōu)于許多公開報道的同類微波介質(zhì)陶瓷，具有實際應用潛力。在10Kg擴大試驗中，此微波介質(zhì)陶瓷的性能優(yōu)異且穩(wěn)定，，經(jīng)相關(guān)廠家驗證此新型微波介質(zhì)具有商業(yè)化應用潛力。 3.為了滿足LTCC技術(shù)要求，通過摻雜低溫燒結(jié)助劑BaCu(B_2O_5)，使BaTi_4O_9-BaZn_2Ti_4O_(11)微波介質(zhì)陶瓷燒結(jié)溫度降低至900℃。摻雜BaCu(B_2O_5)會導致部分BaTi_4O_9相分解為Ba4Ti13O30，以及新雜相BaTi(BO3)2生成。BaCu(B_2O_5)摻雜也能形成液相燒結(jié)機制，并在900℃燒結(jié)可以獲得相對致密的微觀結(jié)構(gòu)。摻雜11wt%BaCu(B_2O_5)并在900℃燒結(jié)2h獲得的0.85BaTi_4O_9-0.15BaZn_2Ti_4O_(11)介質(zhì)陶瓷有較好的微波介電性能：ε_r=30.9， Q×f=20200GHz，τ_f=+11.7ppm/℃。此微波介電性能相較于其他BaO-ZnO-TiO_2三元基低燒微波介質(zhì)陶瓷具有優(yōu)勢，特別是Q×f值相對較高。 4.純ZrTi_2O_6-ZnNb_2O_6微波介質(zhì)陶瓷在空氣中燒結(jié)，會有失氧化學反應，致使其Q×f值非常低。通過摻雜變價元素Mn離子取代Ti~(4+)，會導致原料中TiO2相被遺留下來，構(gòu)成第二雜相；還能促進晶粒生長。受益于Mn離子的受主作用，摻雜0.7wt%MnCO3的樣品在空氣中燒結(jié)具有最大Q×f=44800GHz，高出在空氣中燒結(jié)的純樣品的Q×f值15倍以上。最終，摻雜0.7wt%MnCO3的0.69ZrTi_2O_6-0.31ZnNb2O6介質(zhì)陶瓷可在1270℃的空氣中燒結(jié)7h致密，且具有良好的微波介電性能：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)固溶體微波介質(zhì)陶瓷的晶相組成、微觀結(jié)構(gòu)和微波介電性能。復合離子(Zn_(1/3)Nb_(2/3))~(4+)可全部固溶進入Zr-Ti晶相，當x=0.5~0.8時，形成純ZrTi_2O_6固溶體單相區(qū)。在此單相區(qū)，隨著x值增加，陶瓷樣品的介電常數(shù)從ε_r=43.0連續(xù)下降到ε_r=39.2，τ_f值從τ_f=-10.2ppm/℃減小到τ_f=-25.5ppm/℃， Q×f值從40900GHz增加到43200GHz。 Q×f值增加是由于復合離子(Zn_(1/3)Nb_(2/3))~(4+)對Ti~(4+)離子取代增強了ZrTi_2O_6晶相中的共價鍵作用。最后，Zr(Zn_(1/3)Nb_(2/3))_(0.6)Ti_(1.4)O_6+0.3wt%MnCO_3陶瓷在1260℃空氣中燒結(jié)6h，可獲得致密的微觀結(jié)構(gòu)，為純Zr(Zn_(1/3)Nb_(2/3))_xTi_(2-x)O_6固溶體單晶相，而且具有好的微波介電性能：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 /.
【學位授予單位】：電子科技大學
【學位級別】：博士
【學位授予年份】：2013
【分類號】：TM28
本文編號：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 /.
【學位授予單位】：電子科技大學
【學位級別】：博士
【學位授予年份】：2013
【分類號】：TM28
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