@article{oai:nagasaki-u.repo.nii.ac.jp:00015663, author = {小山田, 了三 and 萩原, 尚男}, issue = {992}, journal = {窯業協會誌, Journal of the Ceramic Association, Japan}, month = {Apr}, note = {ガラス状PbO-GeO2系及びPbO-B2O3系ラマンスペクトルを測定し、これを解析した。ガラス状純GeO2において、バンドは300~600(ピーク位置は410)、760、860及び970cm-1に観測された。410、760及び860cm-1バンドをそれぞれ、4面体構造でTd対称をもつGeO4単位のv4, v1及びv3モードに帰属した。PbO-GeO2系においては、新しいバンドが750~850cm-1に現れ、このバンドは偏光分析により2個のバンドに分けられる。この新しいバンドの一つ、高エネルギー側のバンドは、添加PbO量の増加に伴い低波数側へシフトする。この波数はPbO・GeO2組成の近傍ではほぼ一定の値を示す。更に低エネルギー側のバンドの同様なシフトも観測された。これは正方晶GeO2(ルチル型)のような6配位Ge原子の生成に関係するものと思われる。ラマンスペクトルにおけるこのようなバンドのシフトの傾向は、既報の赤外線吸収スペクトルのバンドのシフトと同様である。ガラス状B2O3において、バンドは450, 650, 806, 1260及び1470cm-1に観測された。650, 806, 1260及び1470cm-1のバンドを、それぞれ平面三角形構造でDsh対称をもつBO3単位のv4', v1', v3'及びv3'振動モードに帰属した。PbO-B2O3系においては、添加PbO量の増加に伴いPbO 30mol%では1350cm-1に、PbO 70mol%では1245cm-1となる。これはPb2+イオン及びBO3群間の相互作用効果を示唆していると考えられる。また1000~1150cm-1に新しいバンドが現れた。バンドの強度はPbO濃度約50mol%までは増加し、それ以上では減少する。この事実はこの系に存在するBO4単位の数と関連づけて考えられる。上述の帰属に基づいてGeO4及びBO3構造単位の力の定数をGFマトリックス法で算出した。GeO4のfr, fφ及びfrφの値はそれぞれ5.45, 0.55及び0.13(mdyn/Å)であり、BO3についてはそれぞれ6.13, 0.80及び0.76(mdyn/Å)であった。, Raman spectra of glassy PbO-GeO2 and PbO-B2O3 systems were measured and analyzed. For pure glassy GeO2, several bands were observed at 300~600(peak position: 410), 760, 860 and 970cm-1. The bands at 410, 760 and 860cm-1 were assigned respectively to v4, v1 and v3 mode of the vibration of the tetrahedral GeO4 which has Td symmetry. For PbO-GeO2 sysmte a new band appeared at 750~850cm-1 and it could be separated into two bands by the polarization analysis. one of these new bands, the band of higher energy, corresponding to the band at 860cm-1 of glassy GeO2, was found to shift toward a lower wavenumber with increasing PbO content. The wavenumber of this band showed a nearly constant value in the neighbourhood of PbO・GeO2 composition. The similar shift of another band of lower energy was aslo found. The fact might be related to the 6-folded coordication of Ge in tetragonalGeO2 (rutile type). Such a trend of band shifting found in Raman spectra is similar to that of the infrared absorption spectra previously reported by the authors. For pure glassy B2O3, several bands were also observed at 450, 650, 806, 1260 and 1470cm-1. The bands at 650, 806, 1260 and 1470cm-1 were assigned respectively to v4', v1', v3' and v3' mode of the vibration of the triangular BO3 which is D3h symmetry. For PbO-B2O3 sysmte, the bands at 1260 and 1470cm-1 were united into a broad band and showed the shift toward a lower wavenumber with increasing PbO content, e.g. 1350cm-1 for PbO 30mol% and 1245cm-4 for PbO 70mol%, suggesting the effect of the interaction between Pb2+ ion and BO3 group. A new band appeared at 1000~1150cm-1, and could be assigned to v3 mode of BO4 tetrahedral structure (Td symmetry). The intensity of this band increased up to about PbO 50mol%, and then decreased with further increase of PbO. The fact might be related to the number of BO4 structural units which are found in the system. Based on the above assignments we estimated the force constants in GeO4 and BO3 structural units by GF matrix method. The values of fr, fφ and frφ for GeO4 were 5.45, 0.55 and 0.13(mdyn/Å) and for BO3 were 6.13, 0.80 and 0.76(mdyn/Å), respectively., 窯業協会誌, 86(992), pp.151-158; 1978}, pages = {151--158}, title = {ガラス状PbO-GeO_2系及びPbO-B_2O_3系のラマンスペクトル}, volume = {86}, year = {1978} }