GeO2-La2O3-TiO2玻璃的结构、热学和光学性质

doi:10.15541/jim20230068

无机材料学报 ›› 2023, Vol. 38 ›› Issue (10): 1230-1236.DOI: 10.15541/jim20230068 CSTR: 32189.14.10.15541/jim20230068

GeO₂-La₂O₃-TiO₂玻璃的结构、热学和光学性质

万家宝¹(), 张明辉²(), 苏怀宇², 曹枝军², 刘学超², 谢坚生², 王祥远², 时英辉², 王亮², 雷水金¹()

1.南昌大学物理与材料学院, 南昌 330031
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2023-02-10 修回日期:2023-02-24 出版日期:2023-10-20 网络出版日期:2023-03-23
通讯作者: 雷水金, 教授. E-mail: shjlei@ncu.edu.cn;
张明辉，副研究员. E-mail: zhangminghui@mail.sic.ac.cn
作者简介:万家宝(1998-), 男, 硕士研究生. E-mail: jbwan_siccas@126.com

Structural, Thermal, and Optical Properties of GeO₂-La₂O₃-TiO₂ Glasses

WAN Jiabao¹(), ZHANG Minghui²(), SU Huaiyu², CAO Zhijun², LIU Xuechao², XIE Jiansheng², WANG Xiangyuan², SHI Yinghui², WANG Liang², LEI Shuijin¹()

1. School of Physics and Materials Science, Nanchang University, Nanchang 330031, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2023-02-10 Revised:2023-02-24 Published:2023-10-20 Online:2023-03-23
Contact: LEI Shuijin, professor. E-mail: shjlei@ncu.edu.cn;
ZHANG Minghui, associate professor. E-mail: zhangminghui@mail.sic.ac.cn
About author:WAN Jiabao (1998-), male, Master candidate. E-mail: jbwan_siccas@126.com
Supported by:
National Natural Science Foundation of China(21961019);National Natural Science Foundation of China(22265018);Chinese Academy of Sciences(2020256);Science and Technology Committee of Shanghai(20QA1410300);Science and Technology Committee of Shanghai(22511100300);Science and Technology Committee of Shanghai(20511107400);Space Utilization System of China Manned Space Engineering(KJZ-YY-NCL07);National Key Research and Development Program of China(2021YFA0716304)

摘要/Abstract

摘要：

La₂O₃-TiO₂玻璃以其折射率高、光学性能优异，在透镜、光学窗口、光通信等领域具有广阔的应用前景。受限于玻璃形成能力, 人们难以制备出大尺寸La₂O₃-TiO₂玻璃, 这严重限制其应用。本研究通过引入网络形成体GeO₂, 有效提高了玻璃形成能力, 从而可用常规方法制备大尺寸的GeO₂-La₂O₃-TiO₂(GLT)玻璃。差热分析表明, GLT玻璃具有较高的玻璃转变温度和抗析晶性能, 玻璃转变温度T_g和ΔT (ΔT=T_c-onset-T_g)分别大于833和209 ℃。最大折射率为2.06, 在可见光和近红外波段的透过率可达78%。实验还研究了Ti含量对GLT玻璃结构、热学和光学性能的影响。结果表明, 随着钛含量增加, 玻璃的形成能力和热稳定性均减弱。摩尔体积V_m和氧离子极化率α_i的变化趋势与折射率一致。GLT玻璃对开发高性能、轻量化、小尺寸的新型器件具有重要意义。

关键词: 高折射率, 热稳定性, 大尺寸玻璃, 高透过率

Abstract:

La₂O₃-TiO₂ glasses show promising application prospect in fields of lenses, optical windows, and optical communication, owing to their high refractive index and excellent performance. However, this glass cannot be prepared into large size because of its weak glass forming ability, which seriously limits its application. In this study, introducing the network former GeO₂ can effectively improve the glass forming ability, so that large-sized GeO₂-La₂O₃-TiO₂ (GLT) glass can be prepared using conventional methods. Differential thermal analysis shows that GLT glasses have high glass transition temperature (T_g) and strong resistance to precipitation, with T_g and ΔT (T_c-onset-T_g) greater than 833 and 209 ℃, respectively. The refractive index is up to 2.06. The transmittance can reach 78% in the visible and near-infrared wavelength bands. The glass forming ability and thermal stability can be weakened by increasing the content of TiO₂. The molar volume and oxygen electron polarizability exhibit the same variation trends as the refractive index of the samples. This result is important for developing new devices with high performance, light weight, and small size.

Key words: high refractive index, thermal stability, large size glass, high transmittance

中图分类号:

TQ171

万家宝, 张明辉, 苏怀宇, 曹枝军, 刘学超, 谢坚生, 王祥远, 时英辉, 王亮, 雷水金. GeO₂-La₂O₃-TiO₂玻璃的结构、热学和光学性质[J]. 无机材料学报, 2023, 38(10): 1230-1236.

WAN Jiabao, ZHANG Minghui, SU Huaiyu, CAO Zhijun, LIU Xuechao, XIE Jiansheng, WANG Xiangyuan, SHI Yinghui, WANG Liang, LEI Shuijin. Structural, Thermal, and Optical Properties of GeO₂-La₂O₃-TiO₂ Glasses[J]. Journal of Inorganic Materials, 2023, 38(10): 1230-1236.

图/表 7

Fig. 1 DTA curves of GLT-(1-5) glasses (a) DTA curves of the GLT-(1-5) glasses; (b) DTA curve of the GLT-3 glass with inset showing an enlarged view of the glass transition; (c) Glass transition temperature Tg and crystallization onset temperature Tx varied with the change of the glasses composition with inset showing the difference of ΔT (ΔT=Tx−Tg)

Fig. 2 XRD patterns of GLT-(1-5) glasses

Fig. 3 Raman scattering spectra of GLT-(1-5) glasses at room temperature Colorful figure is available on website

Fig. 4 Optical transmittance spectra of GLT-(1-5) glasses (a) UV-Vis; (b) MIR region Colorful figures are available on website

Fig. 5 Refractive index curves (a) of GLT-(1-5) glasses at 300-800 nm wavelength, the dependence (b) of refractive index nd and Abbe number on the TiO2 content Colorful figures are available on website

Fig. 6 Dependence of density of GLT-(1-5) glasses on glass compositions

Table 1 Density, molar volume and oxygen ions polarizability of GLT-(1-5) glasses

Sample	TiO₂ content/ % (in mol)	Weight, m/g	True density, ρ/(g·cm^-3)	Molar volume, V_m/(cm³·mol^-1)	Electron polarizability of oxygen, α_O/(×10^-3, nm³)
GLT-1	45	4.8063	5.02	30.06	2.388
GLT-2	47	4.4328	5.06	29.72	2.389
GLT-3	49	4.5602	5.05	29.67	2.406
GLT-4	51	4.2007	5.01	29.86	2.406
GLT-5	53	4.7872	5.00	29.82	2.420

参考文献 34

[1]	XIE J, ZHANG M, GUO R, et al. Investigation of optical and thermal properties in Er³⁺-doped Ga₂O₃-La₂O₃-Ta₂O₅ glasses fabricated by containerless solidification. Journal of Alloys and Compounds, 2021, 872: 159651.
[2]	CAURANT D, GOURIER D, PRASSAS M. Electron-paramagnetic- resonance study of silver halide photochromic glasses: darkening mechanism. Journal of Applied Physics, 1992, 71(3): 1081. DOI URL
[3]	KANEKO M, YU J, MASUNO A, et al. Glass formation in LaO_3/2-TiO₂ binary system by containerless processing. Journal of the American Ceramic Society, 2012, 95(1): 79. DOI URL
[4]	MASUNO A, WATANABE Y, INOUE H, et al. Glass-forming region and high refractive index of TiO₂-based glasses prepared by containerless processing. Physica Status Solidi (c), 2012, 9(12): 2424.
[5]	ZHANG J, ZHANG X, LI Y, et al. High-entropy oxides 10La₂O₃- 20TiO₂-10Nb₂O₅-20WO₃-20ZrO₂ amorphous spheres prepared by containerless solidification. Materials Letters, 2019, 24: 167.
[6]	ARAI Y, ITOH K, KOHARA S, et al. Refractive index calculation using the structural properties of La₄Ti₉O₂₄ glass. Journal of Applied Physics, 2008, 103(9): 094905. DOI URL
[7]	GREEGOR R B, LYTLE F W, SANDSTROM, et al. Investigation of TiO₂-SiO₂ glasses by X-ray absorption spectroscopy. Journal of Non-Crystalline Solids, 1983, 55(1): 27. DOI URL
[8]	CORMIER L, GASKELL P H, CALAS G, et al. Medium-range order around titanium in a silicate glass studied by neutron diffraction with isotopic substitution. Physical Review B, 1998, 58(17): 11322. DOI URL
[9]	FARGES F, BROWN G E, NAVROTSKY A, et al.Coordination chemistry of Ti(IV) in silicate glasses and melts: II. Glasses at ambient temperature and pressure. Geochimica et Cosmochimica Acta, 1996, 60(16): 3039. DOI URL
[10]	DUOERKUN G, ZHANG Y, SHI Z, et al. Construction of n-TiO₂/ p-Ag₂O junction on carbon fiber cloth with VIS-NIR photoresponse as a filter-membrane-shaped photocatalyst. Advanced Fiber Materials, 2020, 2(1): 13. DOI
[11]	SUN Y, MWANDEJE J B, WANGATIA L M, et al. Enhanced photocatalytic performance of surface-modified TiO₂ nanofibers with rhodizonic acid. Advanced Fiber Materials, 2020, 2(5): 118. DOI
[12]	MAO Z Z, DUAN J, ZHENG X J, et al. Study on optical properties of La₂O₃-TiO₂-Nb₂O₅ glasses prepared by containerless processing. Ceramics International, 2015, 41(Sl): S51.
[13]	LI Y, ZHANG X, QI X, et al. High refractive index LaGaO₃-TiO₂ amorphous spheres prepared by containerless solidification. Materials Letters, 2018, 215: 148.
[14]	HAN J, WANG Z, LI J, et al. Large-sized La₂O₃-TiO₂ high refractive glasses with low SiO₂fraction by hot-press sintering. International Journal of Applied Glass Science, 2019, 10(3): 371. DOI URL
[15]	HUANG S J, XIAO Y B, LIU J L, et al. Nd³⁺-doped antimony germanate glass for 1.06 μm fiber lasers. Journal of Non- Crystalline Solids, 2019, 518: 10.
[16]	KAMITSOS E I, YIANNOPOULOS Y, KARAKASSIDESN M A, et al. Raman and infrared structural investigation of xRb₂O·(1-x)GeO₂ glasses. The Journal of Physical Chemistry, 1996, 100(28): 11755. DOI URL
[17]	WANG L L, GUO Y Y, GAO C M, et al. Preparation and spectral properties of Ho³⁺/Tm³⁺ co-doped germanium glass active optical fiber material. Proceedings of SPIE--The International Society For Optical Engineering, 2014(9295): 92950F.
[18]	LIU H, GE X, HU Q, et al. A new sight into the glass forming ability caused by doping on Ba-and Ti-site in BaTi₂O₅ glass. Journal of Materials Science & Technology, 2020, 54(19): 112.
[19]	RAJINDER K, ATUL K, MARINA G B, et al. Structural, thermal and optical characterization of co-existing glass and anti-glass phases of xLa₂O₃-(100-x)TeO₂ and 2TiO₂-xLa₂O₃-(98-x)TeO₂ systems. Journal of Non-Crystalline Solids, 2020, 540(C): 120117.
[20]	CHEN D D, LIU Y H, ZHANG Q Y, et al. Thermal stablity and spectroscopic properties of Er³⁺-doped niobium tellurite galsses for broadband amplifiers. Materials Chemistry and Physics of Applied Physics, 2005, 90(1): 78.
[21]	CHUMAKOV A I, MONACO G, FONTANA A, et al. Role of disorder in the thermodynamics and atomic dynamics of glasses. Physical Review B: Condensed Matter & Materials Physics, 2014, 112(2): 025502.
[22]	WANG W H. Dynamic relaxations and relaxation-property relationships in metallic glasses. Progress in Materials Science, 2019, 106(C): 100561.
[23]	ZHANG L Y, LI H, HU L L. Statistical structure analysis of GeO₂ modified Yb³⁺: phosphate glasses based on Raman and FTIR study. Journal of Alloys and Compounds, 2017, 698: 103.
[24]	CAO W, HUANG F, YE R, et al. Structural and fluorescence properties of Ho³⁺ /Yb³⁺ doped germanosilicate glasses tailored by Lu₂O₃. Journal of Alloys and Compounds, 2018, 746: 540.
[25]	FAN X, LI K, LI X, et al. Spectroscopic properties of 2.7 μm emission in Er³⁺ doped telluride glasses and fibers. Journal of Alloys and Compounds, 2014, 615: 475.
[26]	YOSHIHIRO A, DAVIDE C. Determination of combined water in glasses by infrared spectroscopy. Journal of Materials Science Letters, 2004, 9(2): 244. DOI URL
[27]	HARRISON A J. Water content and infrared transmission of simple glasses. Journal of the American Ceramic Society, 1947, 30(12): 362. DOI URL
[28]	HIROTA S, IZUMITANI T. Effect of cations on the inherent absorption wavelength and the oscillator strength of ultraviolet absorptions in borate glasses. Journal of Non-Crystalline Solids, 1978, 29(1): 109. DOI URL
[29]	REN G, CAO W, LEI R, et al. Observation of efficient Er³⁺: ⁴I_11/2 → ⁴I_13/2 transition in highly Er³⁺ doped germanosilicate glass. Ceramics International, 2018, 44(14): 16868. DOI URL
[30]	INOUE H, WATANABE Y, MASUNO A, et al. Effect of substituting Al₂O₃ and ZrO₂ on thermal and optical properties of high refractive index La₂O₃-TiO₂ glass system prepared by containerless processing. Optical Materials, 2011, 33(12): 1853. DOI URL
[31]	ERSUNDU A E, ÇELIKBILEK M, BAAZOUZI M, et al. Characterization of new Sb₂O₃-based multicomponent heavy metal oxide glasses. Journal of Alloys and Compounds, 2014, 615(C): 712.
[32]	DIMITROV V, KOMATSU T. Electronic polarizability, optical basicity and non-linear optical properties of oxide glasses. Journal of Non-Crystalline Solids, 1999, 249(2): 160. DOI URL
[33]	YOSHIMOTO K, MASUNO A, INOUE H, et al. Transparent and high refractive index La₂O₃-WO₃ glass prepared using containerless processing. Journal of the American Ceramic Society, 2012, 95(11): 063520.
[34]	MASUNO A, INOUE H, YU J, et al. Refractive index dispersion, optical transmittance, and Raman scattering of BaTi₂O₅ glass. Journal of Applied Physics, 2010, 108(6): 1081.

GeO₂-La₂O₃-TiO₂玻璃的结构、热学和光学性质

Structural, Thermal, and Optical Properties of GeO₂-La₂O₃-TiO₂ Glasses

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 34

相关文章 15

编辑推荐

Metrics

本文评价

[1]	苗鑫, 闫世强, 韦金豆, 吴超, 樊文浩, 陈少平. Te基热电器件反常界面层生长行为及界面稳定性研究[J]. 无机材料学报, 2024, 39(8): 903-910.
[2]	肖娅妮, 吕嘉南, 李振明, 刘铭扬, 刘伟, 任志刚, 刘弘景, 杨东旺, 鄢永高. Bi₂Te₃基热电材料的湿热稳定性研究[J]. 无机材料学报, 2023, 38(7): 800-806.
[3]	李悦, 张旭良, 景芳丽, 胡章贵, 吴以成. 铈掺杂硼酸钙镧晶体的生长与性能研究[J]. 无机材料学报, 2023, 38(5): 583-588.
[4]	刘丁, 于洋, 米乐, 于云, 宋力昕. 有机/无机杂化室温固化热控涂层的制备[J]. 无机材料学报, 2018, 33(8): 914-918.
[5]	范广新, 刘泽萍, 闻寅, 刘宝忠. 硅烷偶联剂表面处理对LiNi_0.8Co_0.15Al_0.05O₂结构和性能的影响[J]. 无机材料学报, 2018, 33(7): 749-755.
[6]	杨景锋, 王齐华, 王廷梅. 氧化铝气凝胶的合成与性能[J]. 无机材料学报, 2018, 33(3): 259-265.
[7]	张恒飞, 刘为, 雷姣姣, 宋华庭, 漆虹. Pd掺杂量对有机无机杂化SiO₂膜H₂/CO₂分离性能和水热稳定性能的影响[J]. 无机材料学报, 2018, 33(12): 1316-1322.
[8]	王觅堂, 方龙, 李梅, 柳召刚, 胡艳宏, 张晓伟. 稀土掺杂对ZnO-B₂O₃-SiO₂玻璃热稳定性及结构的影响[J]. 无机材料学报, 2017, 32(6): 643-648.
[9]	龙佩青, 刘希涛, 易志国. 制备工艺对(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃无铅压电陶瓷结构与性能的影响[J]. 无机材料学报, 2017, 32(3): 299-304.
[10]	伍青峰, 崔亚娟, 张海龙, 周怡, 兰丽, 王健礼, 陈耀强. 改进共沉淀法以提高三效催化剂中铈锆复合氧化物的热稳定性[J]. 无机材料学报, 2017, 32(3): 331-336.
[11]	谢晓华, 李晓哲, 李为标, 邵光杰, 夏保佳. PET基陶瓷隔膜的制备及性能研究[J]. 无机材料学报, 2016, 31(12): 1301-1305.
[12]	李宪华, 张雷刚, 王雪雪, 于清波. PANI载的孔状g-C₃N₄的界面聚合法制备与光催化性能研究[J]. 无机材料学报, 2015, 30(10): 1018-1024.
[13]	陈辰, 张海斌, 彭述明, 赵林杰, 朱建国. Ti₃AlC₂体材料的高温临氢行为研究[J]. 无机材料学报, 2014, 29(8): 864-868.
[14]	尹冬梅, 屠德阳, 车丙晨, 张芳芳, 林常规, 戴世勋. Sn对Ge-Se-Te玻璃结构与光学特性的影响[J]. 无机材料学报, 2014, 29(3): 279-283.
[15]	叶龙强, 张清华, 张雨露, 张欣向, 江波. 耐摩擦和高透过SiO₂/TiO₂/SiO₂-TiO₂增透膜的设计和制备[J]. 无机材料学报, 2012, 27(8): 871-875.