片式极限电流型氧传感器用材料研究
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摘要
随着汽车技术的进步和传感器制造工艺技术的提高,汽车用氧传感器不断的完善发展,其发展前景十分广阔。为克服传统电流型氧传感器的缺点,优化传感器的测试性能,本文研究了用固态电子-离子混合导体作为致密扩散障碍层的极限电流型氧传感器的材料制备。这种氧传感器有更好的氧敏特性,拓宽了传感器的氧测量范围,具有结构简单、响应快、工作可靠、成本低廉等优点,是一种很有前景的极限电流型氧传感器。
本文研究了一种新型的注模成型工艺:将钇稳定的氧化锆粉体按一定比例与有机单体、交联剂、分散剂和增塑剂的水溶液混合,得到高固相含量、低粘度的浆料,滴入少许引发剂和催化剂后注模成型。另外制备了新型极限氧传感器的各部分材料,并且进行了材料的改性,对结果进行了分析。
电解质材料:采用新型的注凝成型工艺,制备出8%摩尔含量的钇掺杂氧化锆基陶瓷材料,1400℃温度下烧结的YSZ陶瓷已变为单一的立方萤石结构,经1500℃烧结后相对密度可达95.1%,并用此方法可将烧结温度降低100～200℃。在掺入Al2O3后样品的收缩率降低,体密度变大,有更好的烧结性能。
扩散层材料:确定了本实验La0.8Sr0.2MnO3样品的烧结温度为1000℃,此时生成La0.8Sr0.2MnO3单一晶相,合成反应基本完成;在1200℃烧结温度下相对密度可以达到97%。在掺Sr实验中随着Sr含量增加,合成La1-xSrxMnO3相对密度降低,烧结性能下降。
导电陶瓷材料:掺杂Al2O3的ZnO陶瓷样品随着掺杂量的增加,电阻率略有降低,在Al2O3质量分数为0.5%时达到最小值,并且电阻率随着烧结温度的升高下降很快。而掺杂Y2O3的ZnO导电陶瓷烧结温度为1000℃时,电阻率最大,达到220Ω·cm;电阻率也随着烧结温度的升高而下降,在整个1000℃～1200℃范围内ZnO导电陶瓷电阻率下降幅度达到90%以上。
With the development of the technology for automobile and manufacture craft of sensors, automobile oxygen sensors are consummating constantly with a wide developing foreground. To overcome the disadvantage of the traditional current type oxygen sensor and optimize the testing performances of sensor, using solid state electronic-ion mixed conductor as the material of the preparation of limiting current oxygen sensor with a dense diffusion barrier is studied in this article. This kind of oxygen sensor has a better oxygen sensitive characteristic then broadened a sensor measures range. It has many merits such as inexpensive, simple structure, respond quickly and work reliable. So it is the one kind of the limiting current oxygen sensor which has a good prospect.
In this thesis, a new gel-casting method has been studied: mix the Y2O3 stabilized ZrO2 powder body with organic monomer, coupler, dispersant and the plasticizing agent according to a certain proportion. Then pour the slurry into a model after drop little initiator and accelerating agent in it. Then it has prepared the materials of each part in the oxygen sensor, carried on the material modification and analyzed the results.
Electrolyte material: prepared the Y2O3 stabilized ZrO2 ceramics by a new gel-casting method. YSZ sintered at 1400℃has became the cubic fluorite structure, and sintered at 1500℃whose relative density can reach 95.1%, using gel-casting method can reduce the sinter temperature by 100～200℃. The samples which mixed with Al2O3 have lower rate of contraction, higher volume density, and good sintering character.
Dense diffusion barrier material: the best sintering temperature of La0.8Sr0.2MnO3 material is determined 1000℃, synthetic reaction can finish at this temperature. The samples sintered at 1200℃whose relative density can reach 97%. As increasing of strontium in La1-xSrxMnO3, the volume density of the samples decrease and the sintering character descend.
Conductive ceramics material: the electrical resistivity of ZnO ceramic will decrease slowly when increasing of the Al2O3, and the electrical resistivity reaches the least when the quality percent of Al2O3 is 0.5%; and the electrical resistivity descend quickly when the sintering temperature raise up. The electrical resistivity of ZnO conductive ceramic mixed with Y2O3 sintered at 1000℃is the biggest which reaches 220Ω·cm . And the electrical resistivity descend when the sintering temperature raise up. When the sintering temperature between 1000℃and 1200℃, the electrical resistivities of the ZnO samples fall over 90%.
本文研究了一种新型的注模成型工艺:将钇稳定的氧化锆粉体按一定比例与有机单体、交联剂、分散剂和增塑剂的水溶液混合,得到高固相含量、低粘度的浆料,滴入少许引发剂和催化剂后注模成型。另外制备了新型极限氧传感器的各部分材料,并且进行了材料的改性,对结果进行了分析。
电解质材料:采用新型的注凝成型工艺,制备出8%摩尔含量的钇掺杂氧化锆基陶瓷材料,1400℃温度下烧结的YSZ陶瓷已变为单一的立方萤石结构,经1500℃烧结后相对密度可达95.1%,并用此方法可将烧结温度降低100～200℃。在掺入Al2O3后样品的收缩率降低,体密度变大,有更好的烧结性能。
扩散层材料:确定了本实验La0.8Sr0.2MnO3样品的烧结温度为1000℃,此时生成La0.8Sr0.2MnO3单一晶相,合成反应基本完成;在1200℃烧结温度下相对密度可以达到97%。在掺Sr实验中随着Sr含量增加,合成La1-xSrxMnO3相对密度降低,烧结性能下降。
导电陶瓷材料:掺杂Al2O3的ZnO陶瓷样品随着掺杂量的增加,电阻率略有降低,在Al2O3质量分数为0.5%时达到最小值,并且电阻率随着烧结温度的升高下降很快。而掺杂Y2O3的ZnO导电陶瓷烧结温度为1000℃时,电阻率最大,达到220Ω·cm;电阻率也随着烧结温度的升高而下降,在整个1000℃～1200℃范围内ZnO导电陶瓷电阻率下降幅度达到90%以上。
With the development of the technology for automobile and manufacture craft of sensors, automobile oxygen sensors are consummating constantly with a wide developing foreground. To overcome the disadvantage of the traditional current type oxygen sensor and optimize the testing performances of sensor, using solid state electronic-ion mixed conductor as the material of the preparation of limiting current oxygen sensor with a dense diffusion barrier is studied in this article. This kind of oxygen sensor has a better oxygen sensitive characteristic then broadened a sensor measures range. It has many merits such as inexpensive, simple structure, respond quickly and work reliable. So it is the one kind of the limiting current oxygen sensor which has a good prospect.
In this thesis, a new gel-casting method has been studied: mix the Y2O3 stabilized ZrO2 powder body with organic monomer, coupler, dispersant and the plasticizing agent according to a certain proportion. Then pour the slurry into a model after drop little initiator and accelerating agent in it. Then it has prepared the materials of each part in the oxygen sensor, carried on the material modification and analyzed the results.
Electrolyte material: prepared the Y2O3 stabilized ZrO2 ceramics by a new gel-casting method. YSZ sintered at 1400℃has became the cubic fluorite structure, and sintered at 1500℃whose relative density can reach 95.1%, using gel-casting method can reduce the sinter temperature by 100～200℃. The samples which mixed with Al2O3 have lower rate of contraction, higher volume density, and good sintering character.
Dense diffusion barrier material: the best sintering temperature of La0.8Sr0.2MnO3 material is determined 1000℃, synthetic reaction can finish at this temperature. The samples sintered at 1200℃whose relative density can reach 97%. As increasing of strontium in La1-xSrxMnO3, the volume density of the samples decrease and the sintering character descend.
Conductive ceramics material: the electrical resistivity of ZnO ceramic will decrease slowly when increasing of the Al2O3, and the electrical resistivity reaches the least when the quality percent of Al2O3 is 0.5%; and the electrical resistivity descend quickly when the sintering temperature raise up. The electrical resistivity of ZnO conductive ceramic mixed with Y2O3 sintered at 1000℃is the biggest which reaches 220Ω·cm . And the electrical resistivity descend when the sintering temperature raise up. When the sintering temperature between 1000℃and 1200℃, the electrical resistivities of the ZnO samples fall over 90%.
引文
[1]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[2]王常珍.固体电解质和化学传感器.北京:冶金工业出版社,2000. 603～607.
[3] Kohsi Ishibashi ,Takafumi Kashima,Akiyoshi Asada. Planar type of limiting current oxygen sensors . Sensors and Actuators B ,1993 ,13～14 :41～44.
[4]吴兴惠,王彩君.传感器与信号处理.北京:电子工业出版社,1998.305～308.
[5]徐廷献,沈继跃,薄占满,等.电子陶瓷材料.天津:天津大学出版社,1993.33～35.
[6]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[7]田明原,施尔畏,等,纳米陶瓷与纳米陶瓷粉末,无机材料学报,1998 ,13(2) :129～137.
[8]夏正才,唐超群,潘小龙,等.固体氧化物燃料电池材料研究进展.功能材料, 1997 , 28 (5) : 455.
[9] Xu Yulong,Yao Kui,Zhou Xiaohua.Platinum titania oxygen sensors and their sensing mechanisms . Sensors and Actuators B,1993,13-14 :492～494.
[10]杨媚等.致密扩散层极限电流型氧传感器的研究: [北京科技大学硕士论文],2004
[11]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[12] Jonesa,Begleyb,Murphya. Adhesion of microcantilevers subjected to mechanical point loading: modeling and experiments. Journal of the Mechanics and Physics of Solids,2003, (51) : 1601～1622.
[13]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[14] Lee J H. Review on zirconia air-fuel ratio sensors for automotive applications. Mater Sci, 2003, 38: 4247～4257.
[15]夏正才,唐超群,潘小龙.固体氧化物燃料电池材料研究进展.功能材料,1997,28 (5) :455.
[16] Tuller. Semiconduction and mixed ioniceletronic conduction in nonstoichiomet ric oxides: impact and control .Solid State Ionics,1997,94 : 63.
[17]夏定国,魏秋明,朱时珍,等.高温固体氧化物燃料电池中的阴极材料.中国稀土学报, 1994 , 12 (3) : 258.
[18]杨博,张益康.新型界限电流式高温湿度传感器.传感器世界,1996,12: 16～18.
[19]夏正才,唐超群,潘小龙,等.固体氧化物燃料电池材料研究进展.功能材料, 1997 , 28 (5) : 455.
[20] Choy K L, et al . Fabrication of cathode for solid oxide fuel cell using flame assisted vapor deposition technique. Solid State Ionics,1997,96:49.
[21] Fernando Garzon. Dense diffusion barrier limiting current oxygen sensors. Sensors and Actuators B, 1998, 50(6):125～130
[22] Chevalier S, Kilo M, Borchardt G, et al . MOCVD deposition of YSZ on stainless steels . Applied Surface Science ,2003 ,205 :188～195.
[23]杨博,张益康.新型界限电流式高温湿度传感器.传感器世界,1996,12: 16～18.
[24]徐廷献,沈继跃,薄占满,等.电子陶瓷材料.天津:天津大学出版社,1993
[25]简家文,常爱民,杨邦朝,等. 8-mol%钇稳定氧化锆放电等离子烧结体的电学特性研究.中国科学E辑, 2004, 34(9): 979～987.
[26] Lee J H. Review on zirconia air-fuel ratio sensors for automotiveapplications. J Mater Sci, 2003, 38: 4247～4257.
[27] Reidar Tunold, Rolf degard. On the electrochemistry of metal-YSZ single contact electrodes. Solid State Ionics ,2000 ,136 :707～712.
[28]李蔚,高濂,归林华,郭景坤;纳米材料烧结过程晶粒生长的分析.无机材料学报, 2000 , 15(3) :536～540
[29]夏晖等.具有LSM致密扩散障碍层的片式极限电流型氧传感器.无机材料学报,2004,19(2):411～416
[30]王德,贺强,裴力,等.甘氨酸硝酸盐法合成纳米YSZ微粉及其性能.吉林大学学报(理学版) ,2004 ,42 (2) :261.
[31]王常珍.固体电解质和化学传感器.北京:冶金工业出版社,2000. 603～607.
[32] Choy K L, et al . Fabrication of cathode for solid oxide fuel cell using flame assisted vapor deposition technique . Solid State Ionics,1997,96 :49.
[33]曾燮榕.ZrO2基超微粉体和快离子导体的制备.西安:西北工业大学学报, 1993.
[34] Xin Guo, Space charge conduction in yttria and alumina codoped zirconia . Solid State Ionics ,96 (1997) : 247～254
[35] Zhitomirsky I, Pet ric A. Elect rolytic deposition of ZrO2--Y2O3 films. Materials Letters ,2001 ,50 : 189～193.
[36]刘晓梅,李坤,刘江,等. La1-xSrxMnO3 :阴极材料的制备及性能.吉林大学学报(理学版), 1999, (4) : 44.
[37] Garzon F, Raistrick I, Brosha E, et al. Dense diffusion barrier limiting current oxygen sensor, Los Alamos National Laboratory. Preprint Accepted for Publication in Sensors & Actuators .Bm1998.
[38] Sakaki Y, et La1-xSrxMnO3 as the cathode material for solid oxide fuel cells .Solid State Ionics ,1999 ,118～187.
[39]夏长荣,等.多孔La1-xSrxMnO3的制备及表征.功能材料, 2001 , 32 (3) : 269
[40]夏长荣,许大刚,高建峰,等.多孔La1-xSrxMnO3的制备及表征.功能材料, 2001 , 32 (3) : 269
[41] Sakaki Y, et La1-xSrxMnO3 as the cathode material for solid oxide fuel cells .Solid State Ionics ,1999 ,118 (3O4) :187.
[42]夏长荣,许大刚,高建峰,等.多孔La1-xSrxMnO3的制备及表征.功能材料, 2001 , 32 (3) : 269
[43]袁方利,李晋林,徐业彬,等.ZnO基陶瓷的导电性能研究.功能材料,1998 ,29(6) :592～595
[44]徐业彬,王士良. ZnO线性电阻性能研究.功能材料,1994 ,25 (1) :49～53
[45] Brook R J,In :Treatise on Mater. Sci and Tech. 1976 :331～364
[46]石康源,张绪礼,王筱珍,等. ZnO导电陶瓷的微观结构及导电机理.功能材料,1996 ,27(1) :61～63.
[47] David H,Orlando Auciello. A new ceramic forming process gelcasting . Physics Today July,1998, (22) : 877～880
[48]李盛涛,刘辅宜.新型ZnO陶瓷线性电阻材料.功能材料,1996,27(1):55～60
[49]夏晖等.具有LSM致密扩散障碍层的片式极限电流型氧传感器.无机材料学报,2004,19(2):411～416
[50]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[51] Sakaki Y,et La1-xSrxMnO3 as the cathode material for solid oxide fuel cells .Solid State Ionics ,1999 ,118:187.
[52]徐廷献,沈继跃,薄占满,等.电子陶瓷材料.天津:天津大学出版社,1993
[53] Sakaki Y,et al. La1-xSrxMnO3 as the cathode material for solid oxide fuel cells .Solid State Ionics ,1999 :187.
[54]刘晓梅,李坤,刘江,等. La1-xSrxMnO3:阴极材料的制备及性能.吉林大学学报(理学版), 1999 , (4) : 44.
[55] Garzon F, Raistrick I, Brosha E, et al . Dense diffusion barrier limiting current oxygen sensor, Los Alamos National Laboratory.Preprint Accepted for Publication in Sensors & Actuators .Bm,1998.
[56]刘晓梅,李坤,刘江,等. La1-xSrxMnO3 :阴极材料的制备及性能.吉林大学学报(理学版),1999 , (4) : 44.
[57] Sakaki Y, et La1-xSrxMnO3 as the cathode material for solid oxide fuel cells .Solid State Ionics ,1999:187.
[2]王常珍.固体电解质和化学传感器.北京:冶金工业出版社,2000. 603～607.
[3] Kohsi Ishibashi ,Takafumi Kashima,Akiyoshi Asada. Planar type of limiting current oxygen sensors . Sensors and Actuators B ,1993 ,13～14 :41～44.
[4]吴兴惠,王彩君.传感器与信号处理.北京:电子工业出版社,1998.305～308.
[5]徐廷献,沈继跃,薄占满,等.电子陶瓷材料.天津:天津大学出版社,1993.33～35.
[6]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[7]田明原,施尔畏,等,纳米陶瓷与纳米陶瓷粉末,无机材料学报,1998 ,13(2) :129～137.
[8]夏正才,唐超群,潘小龙,等.固体氧化物燃料电池材料研究进展.功能材料, 1997 , 28 (5) : 455.
[9] Xu Yulong,Yao Kui,Zhou Xiaohua.Platinum titania oxygen sensors and their sensing mechanisms . Sensors and Actuators B,1993,13-14 :492～494.
[10]杨媚等.致密扩散层极限电流型氧传感器的研究: [北京科技大学硕士论文],2004
[11]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[12] Jonesa,Begleyb,Murphya. Adhesion of microcantilevers subjected to mechanical point loading: modeling and experiments. Journal of the Mechanics and Physics of Solids,2003, (51) : 1601～1622.
[13]简家文,杨邦朝,张益康.汽车用氧传感器的工作原理及其应用.传感器技术, 2002, 21(3): 55～57.
[14] Lee J H. Review on zirconia air-fuel ratio sensors for automotive applications. Mater Sci, 2003, 38: 4247～4257.
[15]夏正才,唐超群,潘小龙.固体氧化物燃料电池材料研究进展.功能材料,1997,28 (5) :455.
[16] Tuller. Semiconduction and mixed ioniceletronic conduction in nonstoichiomet ric oxides: impact and control .Solid State Ionics,1997,94 : 63.
[17]夏定国,魏秋明,朱时珍,等.高温固体氧化物燃料电池中的阴极材料.中国稀土学报, 1994 , 12 (3) : 258.
[18]杨博,张益康.新型界限电流式高温湿度传感器.传感器世界,1996,12: 16～18.
[19]夏正才,唐超群,潘小龙,等.固体氧化物燃料电池材料研究进展.功能材料, 1997 , 28 (5) : 455.
[20] Choy K L, et al . Fabrication of cathode for solid oxide fuel cell using flame assisted vapor deposition technique. Solid State Ionics,1997,96:49.
[21] Fernando Garzon. Dense diffusion barrier limiting current oxygen sensors. Sensors and Actuators B, 1998, 50(6):125～130
[22] Chevalier S, Kilo M, Borchardt G, et al . MOCVD deposition of YSZ on stainless steels . Applied Surface Science ,2003 ,205 :188～195.
[23]杨博,张益康.新型界限电流式高温湿度传感器.传感器世界,1996,12: 16～18.
[24]徐廷献,沈继跃,薄占满,等.电子陶瓷材料.天津:天津大学出版社,1993
[25]简家文,常爱民,杨邦朝,等. 8-mol%钇稳定氧化锆放电等离子烧结体的电学特性研究.中国科学E辑, 2004, 34(9): 979～987.
[26] Lee J H. Review on zirconia air-fuel ratio sensors for automotiveapplications. J Mater Sci, 2003, 38: 4247～4257.
[27] Reidar Tunold, Rolf degard. On the electrochemistry of metal-YSZ single contact electrodes. Solid State Ionics ,2000 ,136 :707～712.
[28]李蔚,高濂,归林华,郭景坤;纳米材料烧结过程晶粒生长的分析.无机材料学报, 2000 , 15(3) :536～540
[29]夏晖等.具有LSM致密扩散障碍层的片式极限电流型氧传感器.无机材料学报,2004,19(2):411～416
[30]王德,贺强,裴力,等.甘氨酸硝酸盐法合成纳米YSZ微粉及其性能.吉林大学学报(理学版) ,2004 ,42 (2) :261.
[31]王常珍.固体电解质和化学传感器.北京:冶金工业出版社,2000. 603～607.
[32] Choy K L, et al . Fabrication of cathode for solid oxide fuel cell using flame assisted vapor deposition technique . Solid State Ionics,1997,96 :49.
[33]曾燮榕.ZrO2基超微粉体和快离子导体的制备.西安:西北工业大学学报, 1993.
[34] Xin Guo, Space charge conduction in yttria and alumina codoped zirconia . Solid State Ionics ,96 (1997) : 247～254
[35] Zhitomirsky I, Pet ric A. Elect rolytic deposition of ZrO2--Y2O3 films. Materials Letters ,2001 ,50 : 189～193.
[36]刘晓梅,李坤,刘江,等. La1-xSrxMnO3 :阴极材料的制备及性能.吉林大学学报(理学版), 1999, (4) : 44.
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