无机材料学报 ›› 2019, Vol. 34 ›› Issue (8): 885-892.DOI: 10.15541/jim20180514 CSTR: 32189.14.10.15541/jim20180514
张丽艳1,李洪2,胡丽丽1,王亚杰1,3
收稿日期:2018-10-31
修回日期:2019-01-07
出版日期:2019-08-20
网络出版日期:2019-05-22
作者简介:张丽艳(1971-), 女, 副研究员. E-mail: jndxzly@hotmail.com
ZHANG Li-Yan1,LI Hong2,HU Li-Li1,WANG Ya-Jie1,3
Received:2018-10-31
Revised:2019-01-07
Published:2019-08-20
Online:2019-05-22
摘要:
介绍了一种基于玻璃结构性质而建立的玻璃成分(C)-结构(S)-性能(P)的统计模拟方法。分析了常用的成分-性质(C-P)模拟法的局限性以及结构-性质(S-P)模拟法的特点, 并利用磷酸盐激光钕玻璃化学稳定性改良实验比较了C-P与S-P模型的差异, 表明对于组分微调设计, 结构模拟可以给出更好的模拟结果。叙述了C-S-P模型的建模步骤, 通过模拟案例演示了使用C-S与S-P模型反演玻璃成分的具体过程。除常规性质外, C-S-P模拟法还可以对玻璃的光谱激光性质及化学性质等C-P模型难以准确模拟的性质进行预测和模拟。目的是探索一种对玻璃设计普遍适用的, 可以为新型玻璃的研发和玻璃工业生产提供高效、准确设计的便捷模拟方法。
中图分类号:
张丽艳, 李洪, 胡丽丽, 王亚杰. 玻璃成分-结构-性质的“基因结构”模拟法[J]. 无机材料学报, 2019, 34(8): 885-892.
ZHANG Li-Yan, LI Hong, HU Li-Li, WANG Ya-Jie. Structure Modeling of Genes in Glass: Composition-structure-property Approach[J]. Journal of Inorganic Materials, 2019, 34(8): 885-892.
| Sample | WL /(mg?cm-2) | nd | n2 /(×10-13, esu) | α300 ℃/(×10-6, K-1) | Tg/℃ |
|---|---|---|---|---|---|
| BL | 1.29 | 1.50466 | 1.05 | 12.51 | 493.1 |
| S1 | 0.89 | 1.50574 | 0.99 | 12.75 | 471.9 |
| S2 | 1.07 | 1.50650 | 0.99 | 12.56 | 471.6 |
| S3 | 1.30 | 1.50600 | 0.98 | 12.62 | 482.7 |
| S4 | 1.11 | 1.50554 | 0.99 | 12.27 | 486.1 |
| B1 | 0.65 | 1.50734 | 1.00 | 12.53 | 471.1 |
| B2 | 1.04 | 1.50708 | 0.99 | 12.58 | 472.8 |
| B3 | 0.67 | 1.50841 | 0.99 | 12.48 | 476.8 |
| B4 | 1.11 | 1.50814 | 1.01 | 12.04 | 492.2 |
| L1 | 0.79 | 1.50836 | 0.99 | 12.80 | 466.5 |
| L2 | 0.70 | 1.51001 | 1.03 | 12.48 | 476.8 |
| L3 | 0.65 | 1.51165 | 1.06 | 12.60 | 480.4 |
| L4 | 0.69 | 1.51332 | 1.08 | 12.32 | 484.4 |
表1 实验玻璃编号及性质
Table 1 Number of glass samples and their properties
| Sample | WL /(mg?cm-2) | nd | n2 /(×10-13, esu) | α300 ℃/(×10-6, K-1) | Tg/℃ |
|---|---|---|---|---|---|
| BL | 1.29 | 1.50466 | 1.05 | 12.51 | 493.1 |
| S1 | 0.89 | 1.50574 | 0.99 | 12.75 | 471.9 |
| S2 | 1.07 | 1.50650 | 0.99 | 12.56 | 471.6 |
| S3 | 1.30 | 1.50600 | 0.98 | 12.62 | 482.7 |
| S4 | 1.11 | 1.50554 | 0.99 | 12.27 | 486.1 |
| B1 | 0.65 | 1.50734 | 1.00 | 12.53 | 471.1 |
| B2 | 1.04 | 1.50708 | 0.99 | 12.58 | 472.8 |
| B3 | 0.67 | 1.50841 | 0.99 | 12.48 | 476.8 |
| B4 | 1.11 | 1.50814 | 1.01 | 12.04 | 492.2 |
| L1 | 0.79 | 1.50836 | 0.99 | 12.80 | 466.5 |
| L2 | 0.70 | 1.51001 | 1.03 | 12.48 | 476.8 |
| L3 | 0.65 | 1.51165 | 1.06 | 12.60 | 480.4 |
| L4 | 0.69 | 1.51332 | 1.08 | 12.32 | 484.4 |
图1 BL与含SiO2的玻璃拉曼光谱对比(包含测试与拟合谱图对比)及BL拉曼分峰结果细节描述(a~b)为拟合误差, (c)为虚框处的拟合细节
Fig. 1 Raman spectra of BL glass and SiO2 modified glasses, comparing the measured and the simulated spectra (a) along with the corresponding error in detail curve fitting results for BL glass (b), and the fitting detail of gridlines (c) in Fig.1(a)
| No. | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A9 | A10 | A11 |
|---|---|---|---|---|---|---|---|---|---|---|---|
| BL | 3.6 | 29.0 | 6.9 | 8.2 | 13.5 | 1.9 | 15.3 | 8.7 | 6.3 | 4.3 | 2.5 |
| S1 | 4.4 | 27.6 | 8.1 | 9.2 | 13.1 | 0.0 | 14.2 | 9.1 | 7.7 | 4.3 | 2.4 |
| S2 | 3.3 | 36.8 | 6.6 | 6.3 | 14.2 | 0.0 | 12.5 | 9.3 | 5.1 | 4.2 | 1.9 |
| S3 | 4.2 | 28.1 | 7.6 | 7.4 | 14.9 | 0.0 | 13.0 | 10.5 | 7.5 | 4.8 | 2.0 |
| S4 | 3.4 | 19.2 | 10.4 | 6.8 | 13.0 | 3.1 | 18.8 | 8.0 | 9.3 | 5.2 | 2.7 |
| B1 | 3.7 | 27.6 | 7.8 | 7.4 | 13.4 | 2.8 | 12.7 | 10.2 | 5.9 | 7.2 | 1.1 |
| B2 | 3.7 | 29.0 | 6.7 | 8.0 | 13.6 | 1.8 | 15.3 | 8.6 | 6.4 | 4.2 | 2.6 |
| B3 | 3.6 | 29.1 | 10.7 | 4.6 | 16.3 | 2.8 | 15.4 | 10.8 | 5.1 | 6.9 | 0.9 |
| B4 | 3.5 | 28.4 | 8.0 | 3.5 | 16.4 | 2.3 | 17.8 | 7.4 | 5.7 | 5.0 | 1.7 |
| L1 | 3.7 | 27.1 | 7.4 | 8.8 | 12.3 | 2.5 | 13.5 | 11.1 | 5.8 | 5.8 | 1.9 |
| L2 | 3.7 | 27.4 | 7.4 | 8.5 | 12.3 | 2.4 | 12.8 | 11.5 | 5.7 | 6.5 | 1.7 |
| L3 | 3.8 | 27.1 | 7.4 | 9.3 | 11.2 | 2.4 | 16.2 | 10.0 | 6.3 | 4.2 | 2.2 |
| L4 | 5.0 | 23.5 | 9.4 | 9.3 | 11.0 | 2.7 | 13.7 | 11.4 | 6.1 | 6.7 | 1.4 |
表2 拉曼光谱分峰拟合后各分峰的积分面积(A=Area)
Table 2 Integral area of Raman bands derived from the Raman curve fitting (A=Area)
| No. | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A9 | A10 | A11 |
|---|---|---|---|---|---|---|---|---|---|---|---|
| BL | 3.6 | 29.0 | 6.9 | 8.2 | 13.5 | 1.9 | 15.3 | 8.7 | 6.3 | 4.3 | 2.5 |
| S1 | 4.4 | 27.6 | 8.1 | 9.2 | 13.1 | 0.0 | 14.2 | 9.1 | 7.7 | 4.3 | 2.4 |
| S2 | 3.3 | 36.8 | 6.6 | 6.3 | 14.2 | 0.0 | 12.5 | 9.3 | 5.1 | 4.2 | 1.9 |
| S3 | 4.2 | 28.1 | 7.6 | 7.4 | 14.9 | 0.0 | 13.0 | 10.5 | 7.5 | 4.8 | 2.0 |
| S4 | 3.4 | 19.2 | 10.4 | 6.8 | 13.0 | 3.1 | 18.8 | 8.0 | 9.3 | 5.2 | 2.7 |
| B1 | 3.7 | 27.6 | 7.8 | 7.4 | 13.4 | 2.8 | 12.7 | 10.2 | 5.9 | 7.2 | 1.1 |
| B2 | 3.7 | 29.0 | 6.7 | 8.0 | 13.6 | 1.8 | 15.3 | 8.6 | 6.4 | 4.2 | 2.6 |
| B3 | 3.6 | 29.1 | 10.7 | 4.6 | 16.3 | 2.8 | 15.4 | 10.8 | 5.1 | 6.9 | 0.9 |
| B4 | 3.5 | 28.4 | 8.0 | 3.5 | 16.4 | 2.3 | 17.8 | 7.4 | 5.7 | 5.0 | 1.7 |
| L1 | 3.7 | 27.1 | 7.4 | 8.8 | 12.3 | 2.5 | 13.5 | 11.1 | 5.8 | 5.8 | 1.9 |
| L2 | 3.7 | 27.4 | 7.4 | 8.5 | 12.3 | 2.4 | 12.8 | 11.5 | 5.7 | 6.5 | 1.7 |
| L3 | 3.8 | 27.1 | 7.4 | 9.3 | 11.2 | 2.4 | 16.2 | 10.0 | 6.3 | 4.2 | 2.2 |
| L4 | 5.0 | 23.5 | 9.4 | 9.3 | 11.0 | 2.7 | 13.7 | 11.4 | 6.1 | 6.7 | 1.4 |
| n2/(×10-13, esu) | WL/ (mg?cm-2) | Tg/℃ | CTE /(×10-6, K-1) | SiO2/wt% | B2O3/wt% | La2O3 /wt% | RO*/wt% | R2O*/wt% | Al2O3 /wt% | P2O5/wt% | Obj |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1.029 | 0.90 | 486.9 | 12.18 | 2.16 | 2.81 | 0.91 | 13.59 | 10.74 | 11.58 | 59.17 | 0.99 |
| 1.023 | 0.92 | 486.7 | 12.28 | 1.93 | 2.96 | 1.08 | 13.61 | 10.77 | 11.60 | 59.27 | 0.99 |
| 1.027 | 0.88 | 487.0 | 12.26 | 1.89 | 3.04 | 1.27 | 13.59 | 10.74 | 11.58 | 59.15 | 0.98 |
| 1.024 | 0.94 | 488.0 | 12.21 | 2.05 | 2.97 | 0.89 | 13.60 | 10.75 | 11.59 | 59.21 | 0.98 |
| 1.027 | 0.90 | 487.4 | 12.22 | 2.19 | 2.95 | 1.08 | 13.57 | 10.73 | 11.56 | 59.09 | 0.98 |
| 1.027 | 0.93 | 486.0 | 12.28 | 2.03 | 2.78 | 1.21 | 13.62 | 10.77 | 11.60 | 59.30 | 0.98 |
表3 C-S-P模型预测的玻璃成分及相应性质
Table 3 Compositions and properties of the glass predicted by C-S-P model
| n2/(×10-13, esu) | WL/ (mg?cm-2) | Tg/℃ | CTE /(×10-6, K-1) | SiO2/wt% | B2O3/wt% | La2O3 /wt% | RO*/wt% | R2O*/wt% | Al2O3 /wt% | P2O5/wt% | Obj |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1.029 | 0.90 | 486.9 | 12.18 | 2.16 | 2.81 | 0.91 | 13.59 | 10.74 | 11.58 | 59.17 | 0.99 |
| 1.023 | 0.92 | 486.7 | 12.28 | 1.93 | 2.96 | 1.08 | 13.61 | 10.77 | 11.60 | 59.27 | 0.99 |
| 1.027 | 0.88 | 487.0 | 12.26 | 1.89 | 3.04 | 1.27 | 13.59 | 10.74 | 11.58 | 59.15 | 0.98 |
| 1.024 | 0.94 | 488.0 | 12.21 | 2.05 | 2.97 | 0.89 | 13.60 | 10.75 | 11.59 | 59.21 | 0.98 |
| 1.027 | 0.90 | 487.4 | 12.22 | 2.19 | 2.95 | 1.08 | 13.57 | 10.73 | 11.56 | 59.09 | 0.98 |
| 1.027 | 0.93 | 486.0 | 12.28 | 2.03 | 2.78 | 1.21 | 13.62 | 10.77 | 11.60 | 59.30 | 0.98 |
| Sample | Yb3+ (ICP)/ (×1020, ions?cm-3) | σemi/pm2 | Tg/℃ | Stark splitting |
|---|---|---|---|---|
| PS0 | 2.40 | 0.50 | 477 | 639 |
| PS2 | 2.38 | 0.48 | 441 | 651 |
| PS5 | 2.46 | 0.50 | 462 | 769 |
| PS10 | 2.32 | 0.53 | 503 | 786 |
| PS20 | 2.17 | 0.57 | 509 | 814 |
表4 PS玻璃性质
Table 4 Properties of PS glass
| Sample | Yb3+ (ICP)/ (×1020, ions?cm-3) | σemi/pm2 | Tg/℃ | Stark splitting |
|---|---|---|---|---|
| PS0 | 2.40 | 0.50 | 477 | 639 |
| PS2 | 2.38 | 0.48 | 441 | 651 |
| PS5 | 2.46 | 0.50 | 462 | 769 |
| PS10 | 2.32 | 0.53 | 503 | 786 |
| PS20 | 2.17 | 0.57 | 509 | 814 |
图6 设计成分为SiO2=10mol%时对应设计性质(a)和最高模拟意愿对应的P2O5值对应性质(b)的C-P模型图
Fig. 6 Designed results of C-P model (a) Properties with SiO2=10mol%, (b) Properties with P2O5 mol% under the highest aspiration
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