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选取白云鄂博稀选尾矿和粉煤灰为主要原料, 采用熔铸法制备了04 wt%La2O3掺杂的CaO-MgO-Al2O3-SiO2系微晶玻璃. 利用DTA, XRD, SEM, TEM+EDS和性能测试手段研究La3+在白云鄂博稀选尾矿微晶玻璃中的存在形式及其对该微晶玻璃显微结构、抗折强度和耐腐蚀性的影响. 结果表明, La3+以置换固溶方式进入辉石主晶相, 1 wt%的La2O3可促进辉石主晶相形成. 超过1 wt%的La2O3与基础玻璃组分反应生成Ca3La6(SiO4)6第二相, 并与辉石相争夺Ca2+和Si4+离子来阻碍辉石相形成. 添加1 wt% La2O3的微晶玻璃综合性能最优, 其抗折强度和密度分别为198 MPa和3.18 g/cm3.Clarifying the effect of rare earth (RE) elements on the microstructure and properties of glass ceramics is technically and theoretically important for the further development. Thus the glass ceramics of the CaO-Al2O3-MgO-SiO2 with 04 wt% La2O3 are fabricated from Bayan Obo Mine tailing and fly ash by means of the conventional melting method. Effect of the existence form and the concentration variation of La3+ ions on the crystallization behavior, microstructure and properties, such as bending strength, chemical resistance and density of the glass ceramics, are investigated by DTA, XRD, SEM, TEM and EDS. Results show that both the glass transition and crystallization peak temperature of the samples shift to high temperatures with increasing La2O3 content. Augite [Ca(Mg, Al, Fe)(Si, Al)2O6] is the only crystalline phase in all the five samples. Augite crystals in the form of column are distributed uniformly within the residual glass, and their average size is below 100 nm. The crystallinity of augite has been effectively enhanced by the addition of 1 wt% of La2O3. Owing to the similar ion radius of La3+ and Ca2+, Ca2+ ions within augite have been partially substituted by La3+. Such a substitution can serve as one of the key factors to the enhancement of bending strength of the investigated material with 1 wt% of La2O3 because of the stronger bonding energy of La-O than Ca-O. With further increase of La2O3 from 1 to 4 wt%, the Ca3La6 (SiO4)6 secondary phase forms on the boundary between augite grains and residual glass phase in the form of irregular-shaped particles and this in turn hinders the growth of augite crystals. The crystallinity of augite will be decreased gradually since then. Meanwhile, the formation of this La-riched phase (Ca3La6(SiO4)6) may also prevent augite grains from growing through consuming Ca2+ and Si4+ ions which are two key constituent elements of augite grains. Therefore, there are two forms of La3+ ions in the glass ceramics developed from Bayan Obo Mine tailing: one is the substitution of Ca2+ ion by La3+ in augite crystalline phase, and the other is the forming of secondary crystalline phase La-riched Ca3La6 (SiO4)6. The glass ceramic sample with 1 wt% of La2O3 shows the optimum properties. Its density is 3.18 g/cm3, the bending strength is 198 MPa, and the weight loss in 20 wt% NaOH of this sample is lower than 1 wt%.
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Keywords:
- glass ceramic /
- La2O3 /
- existence form /
- mechanical properties
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[10] Li B W, Deng L B, Zhang X F, Jia X L 2013 J. Non-Cryst. Solids 380 103
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[12] Martn M I, Andreola F, Barbieri L, Bondioli F, Lancellotti I, Rincn J M, Romero M 2013 Ceram. Int. 39 2955
[13] Rezvani M, Eftekhari-Yekta B, Solati-Hashjin M, Marghussian V K 2005 Ceram. Int. 31 75
[14] Abdel-Hameed S A M, Elwan R L 2012 Mater. Res. Bull. 47 1233
[15] Wang M T, Cheng J S, LI M, He F, Deng W 2012 Solid State Sci. 14 1233
[16] Li B W, Du Y S, Zhang X F, Jia X L, Zhao M, Chen H 2014 J. Ceram. Process. Res. 15 325
[17] Karamanov A, Pelino M, Salvo M, Metekovits I 2003 J. Eur. Ceram. Soc. 23 1609
[18] Bernardo E, Dattoli A, Bonomo E, Esposito L, Rambaldi E, Tucci A 2011 Int. J. Appl. Ceram. Tec. 8 1153
[19] Zhao T, Qin Y, Wang B, Yang J F 2015 Mater. Sci. Eng. A 620 399
[20] Kokou L, Du J 2012 J. Non-Cryst. Solids 358 3408
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[1] Hu Y B, Qiu J B, Zhou D C, Song Z G, Yang Z W, Wang R F, Jiao Q, Zhou D L 2014 Chin. Phys. B 23 24201
[2] Ma C S, Jiao Q, Li L J, Zhou D C, Yang Z W, Song Z G, Qiu J B 2014 Chin. Phys. B 23 57801
[3] Chen G H, Song J, Kang X L, Yuan C L, Zhou C R 2014 Mater. Lett. 136 302
[4] Chen L, Yu C L, Hu L L, Chen W 2013 J. Non-Cryst. Solids 360 4
[5] Zhang C, Zhao S L, Deng D G, Huang L H, Tian Y, Xu S Q 2014 Ceram. Int. 40 2737
[6] Goel A, Tulyaganov D U, Kharton V V, Yaremchenko A A, Ferreira J M F 2008 Acta Mater. 56 3065
[7] Dong J P, He F, Luo L, Chen W 2007 J. Inorg. Mater. 22 35 (in Chinese) [董继鹏, 何飞, 罗澜, 陈玮 2007 无机材料学报 22 35]
[8] Xiao S G, Yang X L, Ding J W 2009 Acta Phys. Sin. 58 6858(in Chinese) [肖思国, 阳效良, 丁建文 2009 58 6858]
[9] Meng J, Zhao L J, Yu H, Tang L Q, Liang Q, Yu X Y, Tang B Q, Su J, Xu J J 2005 Acta Phys. Sin. 54 1442(in Chinese) [孟婕, 赵丽娟, 余华, 唐莉勤, 梁沁, 禹宣伊, 唐柏权, 苏静, 许京军 2005 54 1442]
[10] Li B W, Deng L B, Zhang X F, Jia X L 2013 J. Non-Cryst. Solids 380 103
[11] Li B W, Du Y S, Zhang X F, Jia X L, Zhao M, Chen H 2013 Trans. Ind. Ceram. Soc. 72 1
[12] Martn M I, Andreola F, Barbieri L, Bondioli F, Lancellotti I, Rincn J M, Romero M 2013 Ceram. Int. 39 2955
[13] Rezvani M, Eftekhari-Yekta B, Solati-Hashjin M, Marghussian V K 2005 Ceram. Int. 31 75
[14] Abdel-Hameed S A M, Elwan R L 2012 Mater. Res. Bull. 47 1233
[15] Wang M T, Cheng J S, LI M, He F, Deng W 2012 Solid State Sci. 14 1233
[16] Li B W, Du Y S, Zhang X F, Jia X L, Zhao M, Chen H 2014 J. Ceram. Process. Res. 15 325
[17] Karamanov A, Pelino M, Salvo M, Metekovits I 2003 J. Eur. Ceram. Soc. 23 1609
[18] Bernardo E, Dattoli A, Bonomo E, Esposito L, Rambaldi E, Tucci A 2011 Int. J. Appl. Ceram. Tec. 8 1153
[19] Zhao T, Qin Y, Wang B, Yang J F 2015 Mater. Sci. Eng. A 620 399
[20] Kokou L, Du J 2012 J. Non-Cryst. Solids 358 3408
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