Transcription of 1．非晶質物質の振動スペクトル（IR Raman）測定と解析
1 - 10 - SiO2, B2O3 IR Raman SiO2 B2O3 X SiO2 SiO4 Si-O-Si B2O3 BO3 BO4 1 OH F -CH3 -NH2 (I) (II) normal mode H2O 3 H2O H2O 1=3655 cm-1 2=3756 cm-1 3=1595 cm-1 O H H Infrared IR Raman - 11 - Selection rule
2 Stretching vibration Bending vibration out-of-plane bending vibration Breathing vibration s-1 (wavenumber) cm-1 cm-1 cm transmission T( ) = I( )/I0 100 2-1 (Absorbance) A( ) = log10(I0/I( )) 2-2 (Absorption coefficient) ( ) = L-1ln (I( )/I0) 2-3 I0 I( ) Raman shift cm-1 -Si-O-Si- 450 cm-1 -Si-O-Si- 1000 cm-1( ) 800 cm-1( ) -P-O-P- -CH3 1360 ~ 1390 cm-1 -CH3 C-H 2800 ~ 3000 cm-1 -CH2-, -CH3 C-OH 1000 ~ 1200 cm-1 -Si-OH 980 cm-1 -P-OH >C=O 1600 ~ 1950 cm-1 >C=C< 1630 ~ 1680 cm-1 -N-H 3400 ~ 3530 cm-1 -NH2 2 -O-H Free-OH 3610 ~ 3635 cm-1 OH 2500 ~ 3300 cm-1 - 12 - (IR, Raman)
3 (IR) (NMR) (Infrared: IR) (Infrared absorption spectroscopy) m 25 m 25 1000 m (=1/ ) cm-1 cm (cm-1) ( ) E (eV) E (eV) = hc = 1240 107 (cm-1)
4 3-1 14,000 4,000cm-1 4,000 400cm-1 400 10cm-1 L I0 dL dI dI dI = I dL 3-2 Lambert-Beer I dL lnI = I + C x = 0 I = I0 C lnI0 ln(I0/I) = L 3-4 I = I0 exp( L) 3-5 A = log10(I/I0) Absorbance ln (I/I0) Optical Density; OD I0 I ( ) L - 13 - = L 1loge(I/I0) 3-6 Absorption Coefficient L cm cm-1 CO2 2439cm-1 667cm-1 CO2 Absorbance 2-2 Absorption coefficient, (cm-1)
5 2-3 3-6 cm Scattering light 1928 i i i 1 i 2 Rayleigh scattering i R R > 0 Raman scattering i R Stokes i R anti- Stokes R Raman Shift - 14 - ( )
6 IUPAC c wavenumber 1cm cm-1 1/c E 1meV = cm-1 E E0cos2 t k r 3-7 B B0cos2 t k r 3-8 k k k k 2 c 3-9 2 E B k B E 3-7 3-8 k E0 Ei Ei0eicos2 t ei P Ei Ei0 eicos2 it 3-10 P Ei polarizability tensor PxPyPz xx xy xz yx yy yz zx zy zz ExEyEz 3-11 - 15 - R R 0 1cos2 Rt 3-12 0 1 R 3-12 3-10 P Ei0 0eico s2 it 12Ei0 1eico s2 i R t 12Ei0 1eico s2 i R t 3-13 P i i R i + R 3-13
7 3-7 R ES R kS R P Ei0 eicos2 St R eS P eS R R ES ES0eSco s2 St kS R 14 0kS2 ReS ei Ei0eSco s2 St kS R 3-14 S S = i S = i R ES 3-14 ki, ei kS, eS IS ISd 116 2 02kS4R2eS ei 2 Ikieid 2 S4 02c4R2eS , ei 2 Ikieid 3-15 Iki,ei ki, ei x,y,z IS S P RPeSzyxkS- 16 - I Scholze -OH -OH Free-OH, band-1: 3,600 cm-1 Strongly hydrogen bonded-OH, band-2: 2,900cm-1 Free-OH Si O H Strongly hydrogen bonded-OH band-2 Si O H.
8 O- Si -OH O-H Free-OH band-2 -OH Scholze 20Na2O-xAl2O3-(80-x)SiO2 band-1 band-2 FT-IR - Si4+ 1 R 12Na2O-10 CaO-78 SiO2 mol% R = (156 + 12 + 10)/78 = (4-1) Z - X Y X + Y = Z X + = R (4-2) SiO4 Z = 4 SiO4 X = 2R 4 Y = 8 2R (4-3) R, X, Y R ~ 2 Al2O3 Al2O3 Free-OH Strongly hydrogen-bonded-OH - 17 - Al3+ AlO4 Al2O3 - Al3+ Na2O-Al2O3-2 SiO2 R R = (1 + 3 + 4)/(2+2) = 2 (4-4) Y 2 20Na2O-xAl2O3-(80-x)
9 SiO2 FT-IR 1680 C (1) L cm 3 (2) 10ml 1 120 C 10 (3) FT-IR Jasco, FT-IR400 TA %T 4000~400 cm-1 1 nm 100 nm/min FT-IR S/N (4) (5) FT-IR R, X, Y Composition R X Y SiO2 2 0 4 Na2O 2 SiO2 1 3 Na2O 1/2 Al2O3 2 SiO2 Na2O Al2O3 SiO2 2 0 4 Na2O SiO2 3 2 2 P2O5 1 3 - 18 - (6) (7) 4000~2000cm-1 0~100 T G3-1 G3 20Na2O-80 SiO2.
10 Jws (8) (9)
