Solubility mechanisms of fluorine in peralkaline and meta-aluminous silicate glasses and in melts to magmatic temperatures 1 1 Associate editor: F. J. Ryerson
Solubility mechanisms of fluorine in peralkaline and meta-aluminous silicate glasses and in melts to magmatic temperatures 1 1 Associate editor: F. J. Ryerson
复制标题
DOI：
10.1016/j.gca.2003.12.015
复制
发表时间：
2004-06
影响因子：
5
通讯作者：
B. Mysen;G. Cody;Ashley Smith
中科院分区：
文献类型：
--
作者：
B. Mysen;G. Cody;Ashley Smith
在Na 2 O-Al 2 O3-SiO2系统中，使用19 F和29 Si MAS NMR以及拉曼光谱法检查了溶解的氟和硅酸盐玻璃（25 ° C）与熔体（至1400 ° C）之间的结构相互作用，作为Al 2 O3含量的函数。约3 mol. % F计算为溶解在这些玻璃和熔体中的NaF。从~（19）F核磁共振谱，鉴定了四种不同的氟化物配合物。它们是（1）Na-F络合物（NF），（2）Na-Al-F络合物（NAF），（3）Na-Al-F络合物（CF），和（4）Al-F络合物（TF），其中Al以6倍配位，并且可能还有4倍配位。后三种类型的配合物可以通过Al-O-Si桥连接到铝硅酸盐网络。随着玻璃和熔体中Al/（Al + Si）的增加，氟化钠络合物（NF）的丰度降低。在偏铝硅酸盐玻璃和熔体中没有检测到NF复合物。NAF、CF和TF复合物共存于过碱性和偏铝硅酸盐玻璃和熔体中。从玻璃的29 Si-NMR谱和玻璃和熔体的拉曼谱可以看出，无铝和贫铝组成的硅酸盐结构由于F的溶解而聚合，这是因为NF络合物从硅酸盐中将Na网络化改性。F在富铝过碱性和偏铝玻璃及熔体中的固溶导致Al-F键合和铝硅酸盐解聚。温度（高于玻璃化转变温度）以类似于其它碱金属硅酸盐和碱金属铝硅酸盐熔体的方式影响熔体中的Qn-物种形成反应2Q3惠Q4 + Q2。溶解F在本研究中使用的浓度水平不影响这种形态反应的温度依赖性。
Structural interaction between dissolved fluorine and silicate glass (25°C) and melt (to 1400°C) has been examined with19F and29Si MAS NMR and with Raman spectroscopy in the system Na2O-Al2O3-SiO2as a function of Al2O3content. Approximately 3 mol.% F calculated as NaF dissolved in these glasses and melts. From19F NMR spectroscopy, four different fluoride complexes were identified. These are (1) Na-F complexes (NF), (2) Na-Al-F complexes with Al in 4-fold coordination (NAF), (3) Na-Al-F complexes with Al in 6-fold coordination with F (CF), and (4) Al-F complexes with Al in 6-fold, and possibly also 4-fold coordination (TF). The latter three types of complexes may be linked to the aluminosilicate network via Al-O-Si bridges. The abundance of sodium fluoride complexes (NF) decreases with increasing Al/(Al + Si) of the glasses and melts. The NF complexes were not detected in meta-aluminosilicate glasses and melts. The NAF, CF, and TF complexes coexist in peralkaline and meta-aluminosilicate glasses and melts. From29Si-NMR spectra of glasses and Raman spectra of glasses and melts, the silicate structure of Al-free and Al-poor compositions becomes polymerized by dissolution of F because NF complexes scavenge network-modifying Na from the silicate. Solution of F in Al-rich peralkaline and meta-aluminous glasses and melts results in Al-F bonding and aluminosilicate depolymerization. Temperature (above that of the glass transition) affects the Qn-speciation reaction in the melts, 2Q3⇔ Q4+ Q2, in a manner similar to other alkali silicate and alkali aluminosilicate melts. Dissolved F at the concentration level used in this study does not affect the temperature-dependence of this speciation reaction.