掺钕磷硅酸盐玻璃的热机械性能及光谱性能研究
文献类型：学位论文
| 作者 | 丁亚军 |
| 学位类别 | 硕士 |
| 答辩日期 | 2016 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 陈伟 |
| 关键词 | 掺钕磷硅酸盐玻璃 耐热冲击性 光谱性质 玻璃结构 |
| 其他题名 | Study on the Thermo-Mechanical and Spectroscopic Properties of Nd-doped Phosphosilicate Glasses |
| 中文摘要 | 磷酸盐玻璃具有稀土离子溶解度高、声子能量适中、受激发射截面大、荧光寿命长、非线性系数小以及能量提取效率高等优点，广泛被用于高峰值功率和高平均功率激光装置。然而，与硅酸盐玻璃相比，磷酸盐玻璃中磷氧四面体的连接程度较低，其耐热冲击性较差，这严重阻碍了高平均功率激光装置的功率和重复频率的提高。为了改善磷酸盐玻璃的耐热冲击性，本文通过在磷酸盐玻璃中引入SiO2，采用熔融冷却法熔制了高质量的磷硅酸盐玻璃。本文在SiO2-P2O5-Al2O3-Li2O-MgO磷酸盐玻璃体系中，通过测量玻璃的热导率、热膨胀系数、断裂韧性和杨氏模量，研究了SiO2对磷酸盐玻璃耐热冲击性的影响，通过J-O理论研究了SiO2对Nd3+离子光谱性质的影响，并通过拉曼红外光谱和NMR谱图研究了SiO2对磷酸盐玻璃结构的影响。 第一章首先介绍了磷酸盐玻璃的研究进展和应用概况。然后以二元磷酸盐玻璃为例详细分析了磷酸盐玻璃的结构，并简要介绍了在磷酸盐玻璃中Nd3+离子的光谱性质和几种商用高平均功率磷酸盐玻璃的热机械性质，在此基础上提出了磷酸盐玻璃的缺点，引出了本文的研究依据和研究思路。 第二章主要介绍了本实验中所使用的研究方法和理论基础，包括样品的制备、各种玻璃性质的测试以及利用J-O理论计算J-O参数和受激发射截面的方法。 第三章采用SiO2取代磷酸盐玻璃中的P2O5成分，研究了SiO2对磷酸盐玻璃物理性质、光学性质、热机械性质、光谱性质和玻璃结构的影响。研究结果表明，SiO2取代P2O5，玻璃的耐热冲击性明显提高，但是SiO2含量太高会导致耐热冲击性的下降。随着SiO2含量的增加，Nd3+离子的发射截面先增加后降低，但是Nd3+离子的发射截面的变化幅度不大，可以认为SiO2取代P2O5对Nd3+离子发射截面的影响是很有限的。随着SiO2含量的增加，玻璃中O/P逐渐增加，拉曼光谱表明，磷酸盐网络逐渐解聚，当SiO2含量小于8 mol%时，磷酸盐网络结构变化不大，当SiO2含量大于8 mol%时，磷酸盐网络明显解聚。 第四章采用SiO2取代磷酸盐玻璃中的Al2O3成分，研究了SiO2对磷酸盐玻璃物理性质、光学性质、热机械性质、光谱性质和玻璃结构的影响。研究结果表明，SiO2取代Al2O3，玻璃的耐热冲击性没有明显改变，但是Nd3+离子的发射截面显著增加。随着SiO2含量的增加，玻璃中O/P逐渐下降，拉曼光谱表明，磷酸盐网络逐渐聚合，当SiO2含量大于12 mol%时，拉曼光谱中P=O振动峰强度明显增加。NMR谱图表明，随着SiO2含量的增加，六配位Si含量逐渐增加。当SiO2含量大于12 mol%时，六配位Si含量有明显的上升，红外光谱表明玻璃中形成了Si-O-P键。 第五章是对本实验所有研究结果的总结，并指出了研究中存在的不足和需要进一步改进的地方。 |
| 英文摘要 | With the good properties of high ion doped concentration, moderate phonon energy, high stimulated emission cross section, long fluorescence lifetime, low nonlinear refractive index, as well as great extraction efficiency, phosphate glasses have been widely used in high-peak-power laser systems and high-average-power laser systems for several decades. However, compared with silicate glasses, the connectivity of phosphate tetrahedrons is relatively low and thermal shock resistance of phosphate glasses is poor, so the power and repetition rate of high-average-power laser systems are limited seriously. To improve the thermal shock resistance of phosphate glasses, through the introduction of SiO2 in phosphate glasses, high-quality phosphosilicate glasses are prepared by the melting and quenching method. In the SiO2-P2O5-Al2O3-Li2O-MgO phosphate glass system, by measuring the thermal conductivity, thermal expansion coefficient, fracture toughness and Young’s modulus of glasses, the influence of SiO2 on the thermal shock resisance of phosphate glasses is studied in the thesis. The effect of SiO2 on the spectroscopic properties of Nd3+ ions is investigated by J-O theory, and the effect of SiO2 on the structure of phosphate glasses is studied by means of Raman spectra, IR spectra and NMR spectra. In Chapter I, the research progress and application status of phosphate glasses are introduced firstly. Then the structure of binary phosphate glasses is discussed in detail. Besides, the spectroscopic properties of Nd-doped phosphate glasses and thermo-mechanical properties of several commercially available high-average-power phosphate glasses are introduced. Based on the drawback of present phosphate glasses, the basis and ideas for the research are proposed in this thesis. In Chapter II, the experimental methods and basic theories, including the preparation procedures of glasses, property measurements, calculation of J-O parameters and stimulated emission cross section by J-O theory are introduced. In Chapter III, using SiO2 to substitute P2O5 in phosphate glasses, effects of SiO2 on the physical, optical, thermo-mechanical, spectroscopic properties of Nd-doped phosphate glasses and glass structure are studied. When SiO2 substitutes P2O5, thermal shock resistance of phosphate glasses increases significantly, but too high SiO2 content will lead to a decline in thermal shock resistance. With the addition of SiO2 stimulated emission cross section increases firstly and then decreases, but it changes little, so the influence of SiO2 on emission cross section is very limited. With the increase of SiO2 content, O/P increases and the Raman spectra shows phosphate network depolymerizes gradually. When the SiO2 content is less than 8 mol%, phosphate network structure changes a little, when the SiO2 content is more than 8 mol%, phosphate network depolymerizes obviously. In Chapter IV, using SiO2 to substitute Al2O3 in phosphate glasses, effects of SiO2 on the physical, optical, thermo-mechanical, spectroscopic properties of Nd-doped phosphate glasses and glass structure are studied. When SiO2 substitutes Al2O3, thermal shock resistance of phosphate glasses has not changed too much. But the emission cross section is obviously increased. With the increase of SiO2 content, O/P decreases and the Raman spectra shows phosphate network polymerizes gradually. When the SiO2 content is more than 12 mol%, the intensity of (P=O)sym increases significantly. The NMR spectra shows the content of six coordinated Si increases with the increase of SiO2 content. When the SiO2 content is more than 12 mol%, the content of six coordinated Si is obviously increased, and the IR spectra shows that the Si-O-P bond is formed in the glass. Chapter V is the summarization of all the results in this dissertation. Besides, we point out the deficiencies in this research, as well as issues that need further studying. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/17025]  |
| 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 | 丁亚军. 掺钕磷硅酸盐玻璃的热机械性能及光谱性能研究[D]. 中国科学院上海光学精密机械研究所. 2016. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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