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Structural studies on molten glasses by an X-ray anomalous scattering

X 射线反常散射对熔融玻璃的结构研究

基本信息

批准号：
04453070
负责人：
YOKO Toshinobu
金额：
$ 4.54万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1993
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453070/
关键词：
Radial Distribution Function Analysis Non-conventional glasses Glass forming range Pair function method Local atomic structure Coordination state Bond distance Nonlinear Optical Effect ガリウムチタン酸塩ガラスガラス化範囲ビスマス鉛バナジウムリン酸塩ガラスガラス融

项目摘要

In recent years, great attention has been paid to "non-conventional glasses" which do not vitrify by themselves but do vitrify on addition of second components. Therefore, these glasses are expected to have properties very different from conventional glasses such as SiO_2 and B_2O_3. In the present study, we focused especially on gallate glasses as nonconventinal glasses. The structure of 4ONa_2O_3・20Ga_2O_3・40TiO_2 glass was investigated on terms of X-ray dadial distribution function (RDF) method. As a result, it was revealed that the unit structure of both Ti^<4+> and Ga^<3+> is tetrahedrally four fold-coordinated in the glass. This result is largely different from the one for the Na_2O・2TiO_2 glass in which TiO_4 tetrahedra and TiO_6 octahedra coexist. This fact clearly explains the difference in glass formation tendency between the above two glasses that the former glass easily vitrify while the latter does not. The Ti-O bondlength also explains this fact. That is, the bondlengths … More of Ti-O and Ga-O are 0.186 nm in the 40Na_2O・20Ga_2O_3・40TiO_2 glass, while that of Ti-O in the Na_2O・2TiO_2 glass is 0.199 nm which is considerably longer compared to the former case.Next, the structure of 50PbO・5OGaO_<1.5> and 80BiO_<1.5>・20GaO_<1.5> glasses were fully investigated by the neutron and X-ray RDF analyzes. In both glasses, Ga^<3+> is tetrahedrally coordinated. Pb^<2+> in the 50PbO・5OGaO_<1.5> glass forms chains consisting of PbO_3 trigonal pyramids and/or PbO_4 tetragonal pyramids as found in the PbSiO_3 alamosite crystal. That is, Pb^<2+> acts as the glass-network former. Contrarily to this, Bi^<3+> in the 80BiO_<1.5>・20GaO_<1.5> takes the coordination states of BiO_5 and/or BiO_6 foming (BiO_5 , BiO_6) _n sheets.Moreover, the V_2O_5-P_2O_5 glasses with different amounts of V^<4+> were studied on the structure by the X-ray diffraction method. It is found that V^<5+> in the glasses are present in the coordination states of both VO_5 trigonal bipyramids and VO_3 tetrahedra.With the use of the solid state detector (SSD) for X-ray introduced in the present study, it has become possible to measure the more precise RDF of glasses in a shorter time, making it possible to analyze the complicated structure of glasses with ease. Less

近年来，“非常规玻璃”受到极大关注，其本身不玻璃化，但在添加第二组分时会玻璃化。因此，这些玻璃有望具有与传统玻璃如SiO_2和B_2O_3截然不同的性能。在本研究中，我们特别关注作为非传统玻璃的没食子玻璃。采用X射线分布函数(RDF)法研究了4ONa_2O_3·20Ga_2O_3·40TiO_2玻璃的结构。结果表明，Ti 4+ 和Ga 3+ 的单元结构在玻璃中均为四面体四重配位。该结果与TiO_4四面体和TiO_6八面体共存的Na_2O·2TiO_2玻璃的结果有很大不同。这一事实清楚地解释了上述两种玻璃之间的玻璃形成倾向的差异，即前者玻璃容易玻璃化，而后者则不易玻璃化。 Ti-O 键长也解释了这一事实。也就是说，40Na_2O·20Ga_2O_3·40TiO_2 玻璃中 Ti-O 和 Ga-O 的键长为 0.186 nm，而 Na_2O·2TiO_2 玻璃中 Ti-O 的键长为 0.199 nm，比前者长得多。接下来，介绍 50PbO·5OGaO_<1.5> 和 50PbO·5OGaO_<1.5> 的结构通过中子和X射线RDF分析对80BiO_<1.5>·20GaO_<1.5>玻璃进行了充分研究。在两种玻璃中，Ga 3+ 都是四面体配位的。 50PbO·5OGaO_<1.5>玻璃中的Pb^<2+>形成由PbO_3三棱锥和/或PbO_4四棱锥组成的链，如在PbSiO_3铝铜矿晶体中发现的那样。即，Pb 2+ 充当玻璃网络形成剂。与此相反，80BiO_<1.5>·20GaO_<1.5>中的Bi^<3+>采用BiO_5和/或BiO_6的配位态，形成(BiO_5，BiO_6)_n片。此外，通过X射线衍射方法研究了不同V^<4+>含量的V_2O_5-P_2O_5玻璃的结构。研究发现玻璃中的V^<5+>以VO_5三角双锥体和VO_3四面体的配位态存在。利用本研究引入的X射线固态探测器(SSD)，可以在更短的时间内测量更精确的玻璃RDF，从而轻松分析玻璃的复杂结构。较少的