网络修饰体对铝硅酸盐系玻璃微观结构的影响:第一性原理分子动力学模拟
|
摘要
铝硅酸盐玻璃体系是玻璃工业中的重要体系,具有较好的化学稳定性、较高的机械强度和低膨胀系数。本文采用第一性原理分子动力学模拟研究了几种网络修饰体对铝硅酸盐系玻璃的微观结构的影响,研究发现当M/Al=1/2(M=Ca,Mg)或者R/Al=1(R=Na,K)时,铝全部转变为铝氧四面体,此时玻璃结构并不像传统理论认为的形成一个完整的三维网络,而是存在一定数量的非桥氧。通过对径向分布函数,键角分布、配位数、Qn等方面的分析,讨论了网络修饰体的性质对Si以及Al的局部环境的影响。研究表明网络修饰体的电场强度(z/r~2)是影响铝硅酸盐玻璃微观结构的主要因素。网络修饰体在提供游离氧使网络解聚的同时,还有积聚断键的作用,并且电场强度越大,积聚作用越强,网络的连贯性越好。
Aluminosilicate glass plays an important role in the glass industry,due to its good chemical stability,mechanical strength,and low coefficient of expansion. The microstructure of aluminosilicate glass with different network modifier cations were studied by ab-initio molecular dynamic simulations. It is found that when the modifier cations M/Al = 1/2 or R/Al = 1( M = Ca~(2+_、Mg~(2+),R = K~+、Na~+),aluminium atoms have almost transformed into [AlO_4]tetrahedrons,but there is a certain number of nonbridging oxygens existed,which is not consistent with previous theory. Based on the analysis of the radial distribution function,the bond angle distribution,coordination number and Qnetc.,the effects of local environmental properties of Si/Al from network modifier are discussed. The results show that the electric field strength( z/r~2) of the network modifier is the main factor influencing the microstructure of aluminosilicate glass. When the network modifier provides free oxygen to break up the network,it also has the effect of attracting broken bonds,and the stronger the electric field is,the stronger the accumulation is,and the better the coherence of the network.
Aluminosilicate glass plays an important role in the glass industry,due to its good chemical stability,mechanical strength,and low coefficient of expansion. The microstructure of aluminosilicate glass with different network modifier cations were studied by ab-initio molecular dynamic simulations. It is found that when the modifier cations M/Al = 1/2 or R/Al = 1( M = Ca~(2+_、Mg~(2+),R = K~+、Na~+),aluminium atoms have almost transformed into [AlO_4]tetrahedrons,but there is a certain number of nonbridging oxygens existed,which is not consistent with previous theory. Based on the analysis of the radial distribution function,the bond angle distribution,coordination number and Qnetc.,the effects of local environmental properties of Si/Al from network modifier are discussed. The results show that the electric field strength( z/r~2) of the network modifier is the main factor influencing the microstructure of aluminosilicate glass. When the network modifier provides free oxygen to break up the network,it also has the effect of attracting broken bonds,and the stronger the electric field is,the stronger the accumulation is,and the better the coherence of the network.
引文
[1]HUANG C,BEHRMAN E C.Structure and properties of calcium aluminosilicate glasses[J].J Non-Cryst Solids,1991,128(3):310-321.
[2]田英良,李俊杰,杨宝瑛,等.化学增强型超薄碱铝硅酸盐玻璃发展概况与展望[J].燕山大学学报,2017,41(4):283-292.TIAN Y L,LI J J,YANG B Y,et al.Development and prospect of chemically strengthened ultra-thin alkali alumina silicate glass[J].Journal of Yanshan University,2017,41(4):283-292.
[3]刘其军,刘正堂,冯丽萍.闪锌矿型Cd Se电子结构和光学性质的研究[J].燕山大学学报,2010,34(1):29-33.LIU Q J,LIU Z T,FENG L P.Study on electronic structure and optical properties of zinc blende Cd Se[J].Journal of Yanshan University,2010,34(1):29-33.
[4]ZACHARIASEN W H.The atomic arrangement in glass[J].Am Chem Soc,1932,44(10):3841-3851.
[5]LINES M E.A possible non-halide route to ultralow loss glasses[J].J Non-Cryst Solids,1988,103(2):279-288.
[6]LINES M E,MCCHESNEY J B,Calcium aluminate glass as potential ultralow-loss optical-materials at 1.5-1.9μm[J].J Non-Cryst Solids,1989,107(2):251-260.
[7]STEBBINS J F,XU Z.NMR evidence for excess non-bridging oxygen in an aluminosilicateglass[J].Nature,1997,390(6655):60-62.
[8]田英良,孙诗兵.新编玻璃工艺学[M].北京:中国轻工业出版社,2011:16-17.TIAN Y L,SUN S B,Newly organized glass technology[M].Beijing:China Light Industry Press,2011:16-17.
[9]MYSEN B O.Structure and properties of silicate melts[J]Developments in Geochemistry,1989(7):111-112.
[10]WU Y Q,HOU H Y,CHEN H,et al.Coordination and bond properties of Al and Si ions in system of Al2O3-Si O2melts[J].Trans Nonferrous Met Soc China,2001,11(6):965-971.
[11]徐利莹.铝硅酸钙溶体中氧原子的配位性质及动力学[J].硅酸盐学报,2006,34(9):1117-1123.XU L Y.Coordination properties and kinetics of xxygenatoms in calcium auminosilicatesolution[J].Journal of the Chinese Ceramic Society,2006,34(9):1117-1123
[2]田英良,李俊杰,杨宝瑛,等.化学增强型超薄碱铝硅酸盐玻璃发展概况与展望[J].燕山大学学报,2017,41(4):283-292.TIAN Y L,LI J J,YANG B Y,et al.Development and prospect of chemically strengthened ultra-thin alkali alumina silicate glass[J].Journal of Yanshan University,2017,41(4):283-292.
[3]刘其军,刘正堂,冯丽萍.闪锌矿型Cd Se电子结构和光学性质的研究[J].燕山大学学报,2010,34(1):29-33.LIU Q J,LIU Z T,FENG L P.Study on electronic structure and optical properties of zinc blende Cd Se[J].Journal of Yanshan University,2010,34(1):29-33.
[4]ZACHARIASEN W H.The atomic arrangement in glass[J].Am Chem Soc,1932,44(10):3841-3851.
[5]LINES M E.A possible non-halide route to ultralow loss glasses[J].J Non-Cryst Solids,1988,103(2):279-288.
[6]LINES M E,MCCHESNEY J B,Calcium aluminate glass as potential ultralow-loss optical-materials at 1.5-1.9μm[J].J Non-Cryst Solids,1989,107(2):251-260.
[7]STEBBINS J F,XU Z.NMR evidence for excess non-bridging oxygen in an aluminosilicateglass[J].Nature,1997,390(6655):60-62.
[8]田英良,孙诗兵.新编玻璃工艺学[M].北京:中国轻工业出版社,2011:16-17.TIAN Y L,SUN S B,Newly organized glass technology[M].Beijing:China Light Industry Press,2011:16-17.
[9]MYSEN B O.Structure and properties of silicate melts[J]Developments in Geochemistry,1989(7):111-112.
[10]WU Y Q,HOU H Y,CHEN H,et al.Coordination and bond properties of Al and Si ions in system of Al2O3-Si O2melts[J].Trans Nonferrous Met Soc China,2001,11(6):965-971.
[11]徐利莹.铝硅酸钙溶体中氧原子的配位性质及动力学[J].硅酸盐学报,2006,34(9):1117-1123.XU L Y.Coordination properties and kinetics of xxygenatoms in calcium auminosilicatesolution[J].Journal of the Chinese Ceramic Society,2006,34(9):1117-1123