La_2O_3、Pr_2O_3掺杂SnO_2电极陶瓷材料的制备及其烧结性能的研究
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摘要
SnO_2电极具有优越的高温导电性能,具有对玻璃熔体耐腐蚀、无污染等特性,因此,SnO_2电极几乎可以用于所有玻璃品种的熔制,特别适用于含铅玻璃、光学玻璃等高档玻璃的熔制。由于纯SnO_2本身属于不导电、难烧结的材料,制备SnO_2导电陶瓷首要解决的问题是如何提高SnO_2的导电性能和烧结性能。目前国内SnO_2研究主要集中在气敏陶瓷、压敏陶瓷和导电薄膜等方面,关于SnO_2电极方面的研究很少,国产电极偏中低档,高品质电极主要依赖进口,因此,研究电学性能和烧结性能俱佳的国产二氧化锡电极成为当务之急。
论文研究了原料制备、成型工艺和烧结工艺等方面,建立了一种新的制备SnO_2电极的工艺方法,并且探讨了不同添加剂及其含量对电极性能的影响。根据各种测试结果分析各掺杂元素、掺杂含量、烧结工艺对SnO_2电极性能的影响机理,成功的制备了电阻率和致密度均优于国产电极的新型SnO_2电极。
考虑到纳米粉体的粒径小、比表面能大,可以改善SnO_2电极的烧结;另外化学合成法制备的纳米SnO_2原料纯度高,可以减少工业原料带来的杂质。第二章研究了复合掺杂超细SnO_2粉体的制备。采用共沉淀法制备了单元素La掺杂,La、Sb、Ce、Zn复合掺杂超细SnO_2粉体,运用共滴的方式保证pH值的恒定。由XRD和TEM测试可知,得到的SnO_2为四方晶系金红石结构,粉体呈近球形,晶粒发育完整,组织均匀细小,粒径在10-25nm;掺杂不改变SnO_2的晶型,掺杂元素La含量的增加抑制了SnO_2的结晶。
制备好了粉体,接下来在经历了粉体造粒、干法成型、坯体烘干等过程后得到了复合掺杂SnO_2电极。第三章研究了制备过程中成型压力、烧结温度对样品电阻率的影响,确定成型压力为30Mpa,烧结温度在1300-1400℃时,SnO_2电极电阻率最小。通过添加剂对电阻率的影响发现La_2O_3、Sb_2O_3的掺杂对提高SnO_2电极的电学性能效果显著,并探讨了它们的掺杂导电机理,确定了La_2O_3、Sb_2O_3的最佳掺杂含量为1.5wt%和1.0wt%,该含量下的电阻率为98Ω·cm,远低于国产电极的185Ω·cm。
La_2O_3的掺杂可以很好的改善SnO_2电极的导电性能,为了探索La_2O_3的掺杂量和烧结工艺对SnO_2电极致密化有什么样的影响。第四章研究确定了最佳烧结方案和最高烧结温度;在最佳烧结工艺下考察了La_2O_3掺杂量对SnO_2电极的体积密度和烧结性能的影响,探讨了La_2O_3掺杂致密化机理。结果表明La_2O_3掺杂对提高SnO_2电极的致密度有很大的帮助。随着La_2O_3含量的增加,样品的体积密度先增大后减小。当La_2O_3含量为1.5wt%时,体积密度最好,能达到6.514g·cm~(-3),优于国产电极的6.4g·cm~(-3)。
目前SnO_2电极研究几乎没涉及到掺杂稀土元素Pr,为了研究掺杂Pr对电极性能产生的影响,第五章研究了Pr_2O_3掺杂含量对SnO_2电极性能的影响。发现Pr_2O_3的引入对改善二氧化锡电极的性能并不明显。主要是因为Pr_2O_3的引入使其他元素(Zn、La和Sb)向SnO_2晶体表面富集,破坏了SnO_2晶格的完整性和有序性,导致SnO_2电极难以致密化的同时也使其电阻率迅速上升。
Tin dioxide electrode with excellent electrically-conductive property in high temperature and good corrosion resistance to molten glass and no pollution to environment has extensive application in all kinds of glass electric-melting, especially it could be used to melt top-grade glass such as lead glass and optical glass and so on. Due to pure tin dioxide belongs to material which is not electric and hard to sinter, the chief problem needs to resolve of preparing electric tin dioxide ceramic is how to improve electrical properties and sintering properties of tin dioxide. However, nowadays the studies about tin dioxide are mainly focused on gas sensitivity ceramic, capacitor ceramic and electric films of tin dioxide, the studies about tin dioxide electrode are less, domestic electrodes have low quality and the high quality tin dioxide electrodes are still depended on import, therefore, it is urgent to study the domestic tin dioxide with excellent electrical properties and sintering properties.
In this paper, preparation of powder, forming process and sintering process were studied, a new technics about preparation of SnO_2 electrodes was established, the influence of the different additives and their contents were discussed. According to diversified test results, the influence mechanism of every additive and its content and sintering process were also analyzed, a new type SnO_2 electrode which both had better resistivity and bulk density than domestic electrode was prepared successfully.
Considering nano-scale powder had a good improvement on the sintering of the electrodes, and pure nano-SnO_2 raw material was prepared by co-precipitation method could reduce impurity brought by industrial raw material. Compound doped nano-SnO_2 powders prepared by co-precipitation method were studied in chapter two. SnO_2 powders singly doped by La and mixed doped by La, Sb, Ce and Zn were prepared, keeping the same pH by co-drop mode. The test results of XRD and TEM showed SnO_2 had a rutile structure of the square crystal system; a good growth grain and SnO_2 powder presented like a ball and the grain size was from 10 to 25 nanometers; additive did not change SnO_2 crystal type and the increase of La additive could inhibit the crystallization of SnO_2.
Powders were prepared and next were powders getting wet, forming under normal pressure, drying samples and finally compound doped SnO_2 electrodes were obtained. In chapter three, after studying forming pressure and sintering temperature in the process, I found when the forming pressure was 30Mpa and sintering temperature was between 1300 and 1400℃, SnO_2 electrode had a lowest resistivity. Through the influence of the additives, I also found La_2O_3, Sb_2O_3 doped had a remarkable effect on the electrics performance and discussed the doped theory, the resistivity of electrode which had the best doped contents involved 1.5wt% La_2O_3 and 1.0wt% Sb_2O_3 is 98Ω·cm, it was lower than 185Ω·cm of the domestic electrode.
La_2O_3 doped had a nice improvement on the electrics performance of the SnO_2 electrodes, for researching the effects of the La_2O_3 doped content and sintering process on the densification of the electrodes, the best sintering project and the highest sintering temperature were investigated, the densification theory also was discussed in chapter four, the results showed La_2O_3 doped had a big improvement on the densification of the SnO_2 electrodes. With the increase of La_2O_3 content, the bulk density of samples increased at the beginning then decreased. The best bulk density of sample doping 1.5wt% La_2O_3 was up to 6.514g·cm~(-3), it was better than 6.4 g·cm~(-3) of the domestic electrode.
SnO_2 electrodes research hardly involved doped chemical Pr at the present time, for studying the effect of the Pr doped on the electrodes, the effects of the Pr_2O_3 doped content on the properties of the SnO_2 electrodes in the chapter five. The results showed Pr_2O_3 doped had an unconspicuous improvement on the properties of the SnO_2 electrodes. The reason mainly was doping Pr_2O_3 enriched other elements (Zn, La and Sb) on the SnO_2 crystal surfaces, and destroyed the integrality and regular arrangement SnO_2 crystal, lead to sloppy and loose electrodes at the same time made resistivity increase fast.
论文研究了原料制备、成型工艺和烧结工艺等方面,建立了一种新的制备SnO_2电极的工艺方法,并且探讨了不同添加剂及其含量对电极性能的影响。根据各种测试结果分析各掺杂元素、掺杂含量、烧结工艺对SnO_2电极性能的影响机理,成功的制备了电阻率和致密度均优于国产电极的新型SnO_2电极。
考虑到纳米粉体的粒径小、比表面能大,可以改善SnO_2电极的烧结;另外化学合成法制备的纳米SnO_2原料纯度高,可以减少工业原料带来的杂质。第二章研究了复合掺杂超细SnO_2粉体的制备。采用共沉淀法制备了单元素La掺杂,La、Sb、Ce、Zn复合掺杂超细SnO_2粉体,运用共滴的方式保证pH值的恒定。由XRD和TEM测试可知,得到的SnO_2为四方晶系金红石结构,粉体呈近球形,晶粒发育完整,组织均匀细小,粒径在10-25nm;掺杂不改变SnO_2的晶型,掺杂元素La含量的增加抑制了SnO_2的结晶。
制备好了粉体,接下来在经历了粉体造粒、干法成型、坯体烘干等过程后得到了复合掺杂SnO_2电极。第三章研究了制备过程中成型压力、烧结温度对样品电阻率的影响,确定成型压力为30Mpa,烧结温度在1300-1400℃时,SnO_2电极电阻率最小。通过添加剂对电阻率的影响发现La_2O_3、Sb_2O_3的掺杂对提高SnO_2电极的电学性能效果显著,并探讨了它们的掺杂导电机理,确定了La_2O_3、Sb_2O_3的最佳掺杂含量为1.5wt%和1.0wt%,该含量下的电阻率为98Ω·cm,远低于国产电极的185Ω·cm。
La_2O_3的掺杂可以很好的改善SnO_2电极的导电性能,为了探索La_2O_3的掺杂量和烧结工艺对SnO_2电极致密化有什么样的影响。第四章研究确定了最佳烧结方案和最高烧结温度;在最佳烧结工艺下考察了La_2O_3掺杂量对SnO_2电极的体积密度和烧结性能的影响,探讨了La_2O_3掺杂致密化机理。结果表明La_2O_3掺杂对提高SnO_2电极的致密度有很大的帮助。随着La_2O_3含量的增加,样品的体积密度先增大后减小。当La_2O_3含量为1.5wt%时,体积密度最好,能达到6.514g·cm~(-3),优于国产电极的6.4g·cm~(-3)。
目前SnO_2电极研究几乎没涉及到掺杂稀土元素Pr,为了研究掺杂Pr对电极性能产生的影响,第五章研究了Pr_2O_3掺杂含量对SnO_2电极性能的影响。发现Pr_2O_3的引入对改善二氧化锡电极的性能并不明显。主要是因为Pr_2O_3的引入使其他元素(Zn、La和Sb)向SnO_2晶体表面富集,破坏了SnO_2晶格的完整性和有序性,导致SnO_2电极难以致密化的同时也使其电阻率迅速上升。
Tin dioxide electrode with excellent electrically-conductive property in high temperature and good corrosion resistance to molten glass and no pollution to environment has extensive application in all kinds of glass electric-melting, especially it could be used to melt top-grade glass such as lead glass and optical glass and so on. Due to pure tin dioxide belongs to material which is not electric and hard to sinter, the chief problem needs to resolve of preparing electric tin dioxide ceramic is how to improve electrical properties and sintering properties of tin dioxide. However, nowadays the studies about tin dioxide are mainly focused on gas sensitivity ceramic, capacitor ceramic and electric films of tin dioxide, the studies about tin dioxide electrode are less, domestic electrodes have low quality and the high quality tin dioxide electrodes are still depended on import, therefore, it is urgent to study the domestic tin dioxide with excellent electrical properties and sintering properties.
In this paper, preparation of powder, forming process and sintering process were studied, a new technics about preparation of SnO_2 electrodes was established, the influence of the different additives and their contents were discussed. According to diversified test results, the influence mechanism of every additive and its content and sintering process were also analyzed, a new type SnO_2 electrode which both had better resistivity and bulk density than domestic electrode was prepared successfully.
Considering nano-scale powder had a good improvement on the sintering of the electrodes, and pure nano-SnO_2 raw material was prepared by co-precipitation method could reduce impurity brought by industrial raw material. Compound doped nano-SnO_2 powders prepared by co-precipitation method were studied in chapter two. SnO_2 powders singly doped by La and mixed doped by La, Sb, Ce and Zn were prepared, keeping the same pH by co-drop mode. The test results of XRD and TEM showed SnO_2 had a rutile structure of the square crystal system; a good growth grain and SnO_2 powder presented like a ball and the grain size was from 10 to 25 nanometers; additive did not change SnO_2 crystal type and the increase of La additive could inhibit the crystallization of SnO_2.
Powders were prepared and next were powders getting wet, forming under normal pressure, drying samples and finally compound doped SnO_2 electrodes were obtained. In chapter three, after studying forming pressure and sintering temperature in the process, I found when the forming pressure was 30Mpa and sintering temperature was between 1300 and 1400℃, SnO_2 electrode had a lowest resistivity. Through the influence of the additives, I also found La_2O_3, Sb_2O_3 doped had a remarkable effect on the electrics performance and discussed the doped theory, the resistivity of electrode which had the best doped contents involved 1.5wt% La_2O_3 and 1.0wt% Sb_2O_3 is 98Ω·cm, it was lower than 185Ω·cm of the domestic electrode.
La_2O_3 doped had a nice improvement on the electrics performance of the SnO_2 electrodes, for researching the effects of the La_2O_3 doped content and sintering process on the densification of the electrodes, the best sintering project and the highest sintering temperature were investigated, the densification theory also was discussed in chapter four, the results showed La_2O_3 doped had a big improvement on the densification of the SnO_2 electrodes. With the increase of La_2O_3 content, the bulk density of samples increased at the beginning then decreased. The best bulk density of sample doping 1.5wt% La_2O_3 was up to 6.514g·cm~(-3), it was better than 6.4 g·cm~(-3) of the domestic electrode.
SnO_2 electrodes research hardly involved doped chemical Pr at the present time, for studying the effect of the Pr doped on the electrodes, the effects of the Pr_2O_3 doped content on the properties of the SnO_2 electrodes in the chapter five. The results showed Pr_2O_3 doped had an unconspicuous improvement on the properties of the SnO_2 electrodes. The reason mainly was doping Pr_2O_3 enriched other elements (Zn, La and Sb) on the SnO_2 crystal surfaces, and destroyed the integrality and regular arrangement SnO_2 crystal, lead to sloppy and loose electrodes at the same time made resistivity increase fast.
引文
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