中红外氟碲酸盐玻璃除水机理及材料热稳定性的研究
文献类型：学位论文
| 作者 | 岳静 |
| 学位类别 | 硕士 |
| 答辩日期 | 2015 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 廖梅松 |
| 关键词 | 除羟基,中红外,氟碲酸盐，热稳定性 |
| 其他题名 | Research on the dehydration of tellurite glass and the thermally stability of fluororellurite glass for mid-infrared fiber glass |
| 中文摘要 | 中红外波段在国防、医疗、环境等领域有重要应用。中红外光纤激光器具有高效、紧凑、经济的特点。中红外材料要求材料在中红外波段透过性好，损耗低，性质稳定。碲酸盐玻璃透过窗口到达6 μm，具有非线性系数高，热稳性好等特点，是一种良好的制作中红外光纤激光器的基质材料。作为制作光纤激光器的基础，碲酸盐光纤已经获得了大量的研究，光子晶体光纤也不断被应用于超连续谱、光学参量振荡器（Optical Parametric Oscillation 或OPO）中。到目前为止，碲酸盐玻璃中羟基的存在是光纤产生损耗的一个重要原因，对玻璃光学性质产生干扰影响，使玻璃在中红外波段产生大的损耗。玻璃除水是制作中红外玻璃的关键环节。在除羟基的基础上要保证碲酸盐玻璃材料本身所具备的良好性质不变。本研究课题以制备稳定的低羟基含量碲酸盐光纤材料为目的。内容如下： （1）广泛调研了羟基对重金属氧化物玻璃的光学、光谱学及光纤性质的影响，总结了近年来出现的中红外重金属氧化物玻璃除水方法（气氛保护法、通氧法、引入氟化物、氯化物除水等），对比分析了不同方法的除水效果和研究进展。文献调研促进了实验的方向性，为实验方法提供了思路。 （2）在文献调研的基础上，以TeO2–ZnO–Na2O–La2O3玻璃为基础，研究玻璃除羟基工艺。探讨通氧法、气氛保护法、加入氟化物、空气湿度、物料干燥等因素的除水原理及各个步骤可以获得的除水效果，得到一套有效的玻璃除羟基工艺。结合反应热力学公式，将除水实验中的各个因素反应在公式C=K_0?C_0 〖?P〗^m?A_0^(-1)?exp(E/RT)中，其中K0是一定温度下的反应平衡系数，C0为初始原料中含有的羟基含量，P为水的蒸汽压，以空气湿度来度量，m为大于零的常数。A0为指前因子，E为反应活化能。通过实验发现，物料干燥、干燥的环境、气氛保护等措施对降低羟基含量有显著效果。 （3）研究加入氟化物来降低羟基含量，在氟碲酸盐玻璃的基础上，对玻璃材料进行组分调整，提高氟碲酸盐玻璃的热稳定性。获得了低含水量、热稳定性好的69TeO2–15ZnO–5PbF2–5ZnF2–6Nb2O5玻璃。在加入10% mol的氟化物的时候，羟基吸收系数为0.09cm-1，其Tg为342 ℃。?T(Tx–Tg)为163 ℃，Hruby稳定性判据Kg1=(Tx-Tg)/(Tm-Tx)为6.52，达到一般的氧化物玻璃标准。拉曼光谱表明Nb2O5，WO3和MoO3将不同程度的减轻氟对氟碲酸盐中TeO4基团的破坏作用。氟碲酸盐玻璃稳定性和TeO4基团的完整性有关。 （4）进行光纤制作。在氟碲酸盐玻璃的基础上，使用套管法制备光纤，在408℃进行光纤拉丝实验，初步获得了性能稳定的氟碲酸玻璃光纤。 （5）初步探究了高含氟玻璃的热学性质与结构信息。 |
| 英文摘要 | Mid–infrared regain (2~5μm) has received increasing applications in chemical sensing, environmental monitoring, and remote detection. Fiber lasers possess advantages of compactness, economy, and efficiency over solid–state lasers. As the host material, these glasses require good transmittance, sufficient low material loss, and fine mechanical properties, and thermal stability for optical fiber drawing. Tellurite glass is a mid–infrared material to transmit up to 6μm. The properties of high refractive index, low phonon energy and glass stability make it prior candidate for mid-infrared fiber lasers materials. Therefore, the development of tellurite glass with thermal stability, robustness, and low phonon energy, has attracted the interest of an increasing number of researchers. Yet the water in the glass causes great loss, thus hindering its nonlinear applications in tellurite fiber as supercontinuumand and as fiber lasers source. Therefore, water removal has been the main issue of mid-infrared optical fiber materials. This research focuses on low OH tellurite glass for optical material, aiming to obtain dehydration of the tellurite glass maintaining the good properties. The work is conducted as the following: 1. Effect of hydroxyl groups on the optical, spectroscopic and the optical fiber properties of the mid-infrared heavy metal oxide glass are discussed. The recent widely used process of dehydration techniques (Reaction Atmosphere Process, Budding(RAP) dry gas, Fluoride dehydration, Chloride dehydration etc.) are reviewed comprehensively. As a result, the processing and the direction of dehydration techniques and the design of experiments are proposed. 2. Basing on the glass TeO2–ZnO–Na2O–La2O3, the work investigate the effect of dehydration techniques such as vacuum drying, bubbling the oxygen, Atmosphere protection, Fluorides dehydration, Chlorides dehydration and explain the key procedures related to the significance of thermodynamics in the form of the formula C=K_0?C_0 〖?P〗^m?A_0^(-1)?exp(E/RT). In the formula, K0 is the equilibrium coefficient at a certain temperature, C0 the initial concentration of hydroxyl content in the raw material, P is the vapor pressure of water, indicted by the air humidity, m a positive constant. A0 is the pre-exponential factor, E is the activation energy. 3. The work specially focuses on the Fluorides dehydration and succeeds to improve the thermal stability of fluorotellurite glasses 69TeO2–15ZnO–5PbF2–5ZnF2–6Nb2O5 by some composition modifications. The Tg of fluorotellurite glasses is 342℃, ?T(Tx–Tg) 163℃. Hruby date Kg1=(Tx-Tg)/(Tm-Tx) is 6.52, comparable to the oxides glass. By using the physical dehydration techniques, including the vacuum drying of the raw materials, fabrication at dry atmosphere, high purity oxygen bubbling, the hydroxyl absorption coefficient αOH of the fluorotellurite is 0.05 cm–1, when 10% (mol) fluoride is introduced. Raman spectra indicate that Nb2O5, WO3 and MoO3 will mitigate the destructive effect of fluoride on TeO4 entities. The fluorotellurite glass stability is directly related to the structure of TeO4 groups. 4. Fiber preparations. Based on the fluorine tellurite glass, the work prepared a step-index fiber using way of rod in tube. The fiber drawing is operated at 408 ℃. 5. Thermal properties and structural information of high fluorotellurite glass is initially explored. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/16918]  |
| 专题 | 上海光学精密机械研究所_学位论文 |
| 推荐引用方式 GB/T 7714 | 岳静. 中红外氟碲酸盐玻璃除水机理及材料热稳定性的研究[D]. 中国科学院上海光学精密机械研究所. 2015. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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