Low OH content germanate glass prepared by batch soaking process in CCl 4

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1 Vol.18 No.8 The Chinese Journal of Nonferrous Metals Aug (2008) ( ) CCl 4 40GeO 2-30SiO 2-12Al 2 O 3-6BaO-6CaO-6MgO OH /cm (3.0 µm) Gauss 5 OH 1.71 /cm OH 0.25 /cm DTA XRD OH TB 321 A Low OH content germanate glass prepared by batch soaking process in CCl 4 XIAO Zhuo-hao, CHEN Yuan-yuan, ZUO Cheng-gang, LU An-xian (School of Materials Science and Engineering, Central South University, Changsha , China) Abstract: 40GeO 2-30SiO 2-12Al 2 O 3-6BaO-6CaO-6MgO glass was prepared by using batch soaking process with CCl 4 as dehydration agent. The influence of this process on the infrared transmittance and crystallization behavior of the germanium glass was investigated. The results show that the infrared spectra contains a single band at approximately /cm for the germanate glass. This broad absorption band is deconvoluted into five bands and some possible reasons for each band have been given. The absorption coefficient of hydroxyl in the germanate glass prepared by conventional melt quenching technique is 1.71 /cm while that of the one prepared by batch soaking process in CCl 4 is 0.25 /cm. The analyses of DTA and XRD indicate that the glass prepared by batch soaking process crystallizes at lower temperature and has bigger crystallization rate for the residual chlorine acting as a nucleation agent in the interspaces of the glass network structure. The SEM images show that the residual chlorine promotes the formation of crystallite and changes the shape of the crystallite cluster. Key words: germanate glass; infrared transmittance; crystallization; OH absorption; batch soaking process DENNIS LAUBENGAYER [1] 1926 (JPPT ) axlu@mail.csu.edu.cn

2 [2] [3] [4] (Reaction atmosphere process, RAP [5 8] ) [9 10] [9, 11] [9 10, 12 14] [15] CCl 4 POCl 4 SOCl 2 [16] CCl 4 YANG [8] Er 3+ OH /cm 0.28 /cm ZHAI [17] Nd 2 O 3 Al 2 O 3 -SiO 2 CCl 4 OH WANG [18] CCl 4 OH MARTUCCI [19] SOKOLNICKI [20] LI [11] CCl 4 [21 22] (BSP Batch soaking process) CCl CCl 4 CCl 4 10 min 1 (BSP) Fig.1 Schematic diagram of experimental apparatus for BSP CCl h 2H 2 O+CCl 4 4HCl+CO 2 (1) 2HO + CCl 4 2HCl + CO 2 + 2Cl (2) CCl 4 H 2 O OH H 2 O OH H 2 O GeO 2-30SiO 2-12Al 2 O 3-6BaO-6CaO- 6MgO ( %) GeO 2 5 N 149 µm 200 g 10 h A B A B h h h (IR)

3 mm 15 HOSONO [23] Na 2 O( ) mm 3 mm 240 SiC 0 5% 28% OH 0.06 µm /cm Na 2 O Perkin 5% /cm 28% /cm HALL Elmer Lanbda 900UV/VIS/NIR [24] Na Thermo Nicolet Nexus FT IR 2 O 0~10% OH /cm /cm Na 2 O 400 /cm /cm 10% /cm (DTA) /cm 2 TAS100 DTA 350 /cm 2 10 /min 25~1 000 Gauss X (XRD) 3014 X X 149 µm (SEM) 4%HF 80 s X BSP BSP 2 A B 80% 5 µm /cm OH 2 Fig.2 IR absorption profile of samples A and B 3 OH Fig.3 Spectral deconvolution of IR absorbance of samples A and B: (a) /cm; (1) /cm; (2) /cm; (3) /cm; (4) /cm; (5) /cm A /cm /cm 5 Gauss /cm OH (Fig.4(a)) OH /cm [24] PLOTNICHENKO [25] /cm /cm OH /cm /cm OH (Fig.4(b)) (Fig.4(c)) /cm OH (Fig.4(d)) /cm

4 OH Fig.4 Hydroxyl in different configurations in germanate glass MCMILLAN [26] ENGHOLM [27] IR Raman /cm [21 22] Ge [22, 28 29] Ge O OH Ge O (Fig.4(e)) B OH Gauss /cm /cm BSP OH Lambert-Beer 3 OH OH OH /cm α(oh) OH 1 T0 α(oh) = ln( ) (3) L T L cm T 0 T /cm (3) α(oh) A =1.71 /cm α(oh) B =0.25 /cm BSP OH BSP OH α(oh) 1.71 /cm OH α(oh) 0.25 /cm OH 26.28% 72.41% 2.2 BSP 5 DTA DTA BSP A BSP B BSP 20 OH [2] BSP B OH BSP

5 h Fig.6 Photograph of glass samples at 730 for 1 h 5 DTA Fig.5 DTA curves of glass samples A OH B A DTA BSP OH 5 DTA BSP B 897 B [12] B CCl 4 (2) CCl 4 [30] DTA BSP XRD A B B A 7(a) 730 XRD A A B PDF ( ) (Ge 2 Al 6 O 13 ) XRD BSP XRD 7(b) A B B A B 800 A B MgGeO 3 ( 7(c)) B BaMgSi 900 ( 7(d)) A B BaMgSi 7 B A DTA ( 5) B A 900 B 7(d) A B X XRD 2.3 SEM h 50~80 nm BSP A BSP

6 XRD Fig.7 XRD patterns of glass samples under different thermal condition: (a) 730, 1 h; (b) 750, 1 h; (c) 800, 1 h; (d) 900, 1 h 8 A h SEM Fig.8 SEM photograph of sample A at 730 for 1 h 9 B h SEM Fig.9 SEM photograph of sample B at 730 for 1 h BSP HAN [30] 3 1) CCl 4

7 OH OH 1.71 /cm 0.25 /cm 2) CCl 4 3) CCl 4 REFERENCES [1] DENNIS L M, LAUBENGAYER A W. Germanium XVII: Fused germanium dioxide and some germanium[j]. The Journal of Physical Chemistry, 1926, 30(11): [2] JEWELL J M, SPESS M S, SHELBY J E. Effect of water concentration on the properties of commercial soda-lime-silica glasses[j]. Journal of the American Ceramic Society, 1990, 73(1): [3] CURRIER N W, SEVERRDIA A G, TOTTEN G A. Determination of the variation in the water content across the wall of a fused-silica crucible by transmission Fourier transform infrared spectroscopy[j]. Applied spectroscopy, 1988, 42(6): [4] FANDERLIK J. Silica glass and its application[m]. Amsterdam: Elsevier, [5]. [M]. :, GAN Fu-xi. Modern glass science and technology[m]. Shanghai: Shanghai Science Press, [6]. [D]. :, YANG Gang-feng. Removal of OH groups in Er 3+ doped phosphate glasses by reaction atmosphere process[d]. Guangzhou: South China University of Technology, [7] EBENDORFF-HEIDEPRIEM H, SEEBER W, EHRT D. Dehydration of phosphate glasses[j]. Journal of Non-Crystalline Solids, 1993, 163(1): [8] YANG G F, ZHANG Q Y, ZHAO S Y, DENG Z D, YANG Z M, JIANG Z H. Dehydration of Er 3+ -doped phosphate glasses using reactive agent bubble flow method[j]. Journal of Sol-Gel Science and Technology, 2006, 352(8): [9] KOBAYASHI K. Recovery of hysteresis capacitance-voltage curves of MOS capacitors passivated with bubbled fluoridecontaining glasses[j]. Journal of the European Ceramic Society, 1997, 17: [10] KOBAYASHI K, SASAKI H. Visible rays cutoff and infrared transmission properties of TeO 2 -GeO 2 -V 2 O 5 -PbF 2 glass systems[j]. Journal of the European Ceramic Society, 1999, 19(5): [11] LI W, WILLEY R J. Stability of hydroxyl and methoxy surface groups on silica aerogels[j]. Journal of Non-Crystalline Solids, 1997, 212(2/3): [12],. [J]., 2002, 165(6): FENG Ming-liang, GUO Li-ya. The application of fluoride and chloride in glass production[j]. Glass, 2002, 165(6): [13],,. BaF 2 BaO [J]., 2005, 25(1): CAO Guo-xi, HU He-fang, GAN Fu-xi. Effect of BaF 2 /BaO substitution on the optical properties of barium gallogermanate glass[j]. Acta Optica Sinica, 2005, 25(1): [14],,,. [J]., 2005, 34(6): YUAN Xin-qiang, FAN You-yu, CAO Guo-xi, HU He-fang. Oxyfluoride glass transmitting middle-infrared with large bulk[j]. Infrared and Laser Engineering, 2005, 34(6): [15]. [D]. :, ZHOU Yong-heng. Study on hydroxyl in quartz glass and quartz raw materials[d]. Beijing: China Building Materials Academy, [16],,,,. [J]., 2005, 20(5): YANG Gang-feng, ZHAO San-yin, DENG Zai-de, SUN Jia-sen, JIANG Zhong-hong. Removal of OH groups in Er3+-doped phosphate glasses by reaction atmosphere process[j]. Journal of Inorganic Materials, 2005, 20(5): [17] ZHAI Ji-wei, SHEN Bo, YAO Xi, ZHANG Liang-ying. Preparation and spectral properties of Nd 2 O 3 -doped silica-based glasses prepared by the sol-gel process[j]. Ceramics International, 2002, 28(7): [18] WANG L H, TSAI B J. The sintering and crystallization of colloidal silica gel[j]. Materials Letters, 2000, 43(5/6): [19] MARTUCCI A, BRUSATIN G, GUGLIELMI M, STROHHÖFER C, FICK J, PELLI S, RIGHINI G C. Fabrication and characterization of Sol-Gel GeO 2 -SiO 2 erbium-doped planar waveguides[j]. Journal of Sol-Gel Science and Technology, 1998, 13(1/3): [20] SOKOLNICKI J, URBASK B, LEGENDZIEWICZ J. Investigation of Er, Er:Yb and Er:Tm systems in silica sol-gels[j]. Journal of Alloys and Compounds, 2000, 300/301: [21] HENDERSON G S. The germanate anomaly: What do we know?[j]. Journal of Non-Crystalline Solids, 2007, 353(18/21): [22] OSAKA A, JIANRONG Q, MIURYA Y, TAKESHI Y. EXAFS of

8 germanium in glasses of the GeO 2 -TeO 2 system[j]. Journal of Non-Crystalline Solids, 1995, 191(3): [23] HOSONO H, ABE Y. Temperature dependence of infrared absorption spectra of hydroxyl groups in soda germanates glasses[j]. Journal of the American Ceramic Society, 1989, 72(1): [24] HALL M M, SHELBY J E. Water diffusion and solubility in alkali germanate[j]. Phys Chem Glasses, 2004, 45(5): [25] PLOTNICHENKO V G, SOKOLOV V O, MASHINSKY V M, MASHINSKY V M, SIDOROV V A, GURYANOV A N, KHOPIN V F, DIANOV E M. Hydroxyl groups in germania glass[j]. Journal of Non-Crystalline Solids, 2001, 296(1/2): [26] MCMILLAN P F, REMMELE R L. Hydroxyl sites in SiO 2 glass: A note on infrared and Raman spectra[j]. American Mineralogist, 1986, 71(5/6): [27] ENGHOLM J R, HAPPEK U, SIEVERS A J. Observation of site-dependent relaxation of the OH vibrational stretch mode in fused silica[j]. Chemical Physics Letters, 1996, 249(5/6): [28] HANNON A C, MARTINO D D, SANTOS L F, ALMEIDA R M. A model for the Ge O coordination in germanate glasses[j]. Journal of Non-Crystalline Solids, 2007, 353(18/21): [29] WANG M C, WANG J S, HON M H. Effect of Na 2 O addition on the properties and structure of germanate glass[j]. Ceramics International, 1995, 21(2): [30],,,,. Li 2 O-Al 2 O 3 -SiO 2 [J]., 2006, 34(6): HAN Chen, GUO Xing-zhong, YANG Hui, SONG Fang-fang, CHEN Ming-xing. Crystallization mechanism of Li 2 O-Al 2 O 3 - SiO 2 glass containing fluoride and phosphide[j]. Journal of the Chinese Ceramic Society, 2006, 34(6): ( )