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大田, 英明

Japanese

最近の世界金融危機と新興国経済の変化一何がアジア危機と異なっているのか一

福田, 喜彦

A Framework of Japanese History Lesson Models using the Traditional Industry of Setouchi Sea Areas : Salt Manufacture Business of Japanese Society judging from "Setouchi Jusshu Enden"

松岡, 恵利奈

千代田, 憲子

A Study on the Design of Station and Public Space

小黒, 明日香

富田, 英司

What Conversational Contents Do High School Students Want to Talk with Teachers ?

前川, 尚

1
工学ジャーナル　第 8 巻
2009 年 3 月
Annual Journal of Eng.,
Ehime Univ., VIII, Mar., 2009
原稿受理　平成 20 年 10 月 27 日
酸化物ガラス及びその融体の酸塩基と酸化還元
―ガラスのスペクトロスコピーと融体の熱力学的研究―
Acid-Base and Redox Properties of Oxide Glasses and Their Melts 
Spectroscopic Investigation for Glasses and Thermodynamics of the Melts
1
Takashi MAEKAWA 
The acid –base and redox characteristics of oxide glass and their melts are 
reviewed on the basis of the author’s experimental results concerning the 
spectroscopic investigations on the glasses and electrochemical studies of their 
melts. The results of X-ray fluorescence chemical shifts, radiation induced 
colorization and solid state MAS NMR for the glasses are discussed in terms of the 
basicity of the glasses. The importance of the examination of the redox properties 
of the multivalent ions on the refining process of the glass forming are also shown   
Key-words : Glasses, Acid and base, Redox, X-ray energy, Pulse Radiolysis, NMR, 
Voltammetry 
1．研究の背景
 SiO2, B2O3  Si O Si, B O B
Na2O
3
 [H ]
O2
 [H ] [OH ] = 10 14
pH
                                                 
1 3
 Department of Materials and Biochemistry 
   Graduate School of Science and Technology, Ehime University 
2
Table 1 The Issue to be resolved in the fields of glass chemistry 
- Ideas at beginning of my research- 
Si O Si  A2O  =  2  Si O A A
Discrete
SiO4  Si O
Qn
Table 1
2．本論
1
2 X SiK SiK
3
4 MAS NMR Qn
2.1  Na2O-B2O3 融体への Ag2O の溶解度―― Na2O と Ag2O の塩基度の違い[1]
Ag2O 400
Ag  (1/2) O2  =  Ag2O (in glass) 
K = a(Ag2O) / a(Ag) p(O2)1/2
a(Ag2O) , a(Ag) , p(O2)  Ag2O , Ag Ag 
a(Ag)  1 
a(Ag2O) = K p(O2)1/2
3
1
Fig. 1 
Na2O
1
[Na2O]/[ 2O3] Fig.2 
Na2O
B2O3 Na2O
Ag2O
Na2O
2.2 ガラスの蛍光Ｘ線のケミカルシフトと
光学的塩基度[2],[3]
 X
K 2p  1s
S2
S0 SO32 SO42
K K
X
2.2.1 光学的塩基度とは
Duffy Ingram Tl Pb2 Bi3
Fig. 1 Apparatus for the determination  
of Solubility of Ag2O in glass melts 
Fig. 2 Solubility of Ag2O in Na2O-B2O3
Melts: Oxygen Pressure = 1 atm 
0 0.1 0.2 0.3 0.4 0.5
0
0.1
0.2
0.3
N(Na2O ) / N(B2O3) ratio
So
lu
bi
lit
y 
of
 A
g 2O
, N
(A
g 2
O
)
4
SiO2 B2O3 Si O Si  B O B
Pb2 Na Ca2
B O O2
6s 6p 6s  6p 
6s 6p
th A B ZA ZB
rA B A B
th  = 1  ( ZA rA / 2 )(1  1 / A)  ( ZB rB / 2 )(1  1 / B ) 
A B
A = 1.36 ( A 0.26) 
2.2.2 蛍光 X 線のケミカルシフトと光学的塩基度の関係
 X 2 Si Al P
X
2
X
X
1
2
3
4 5
6
7
8
910
11
12
13
14
15
16
17
18
19
0-0.05-0.10
0
0.5
1.0
1.5
Si K Chemical shift / eV
Si
 K
 C
he
m
ic
al
 sh
ift
 /e
V
100 50 0
SiO2 / mol%
-0.1
0
C
he
m
ic
al
 S
hi
ft
 /e
V
Fig. 3  Chemical shifts of Si K  for binary 
silicate glasses. :Na2O-SiO2, :K2O-SiO2,
:Rb2O-SiO2, :PbO-SiO2, :B2O3-SiO2
Fig. 4  Relation between Si K  and Si K energy shifts for the silicate. The reference material 
is -quartz. 1. -quartz, 2. -cristbalite, 3. Silica glass, 4. -CaSiO3, 5. -CaSiO3, 6.
-CaSiO4, 7. -CaSiO4, 8.Na2Si2O5, 9.Na2Si2O5(glass), 10.Na2SiO3, 11.Na2SiO3(glass), 
12.Na4SiO4, 13.K2Si2O5(glass), 14. Mg2SiO4, 15.ZrSiO4, 16.Mn2SiO4, 17.Al2Si3O9, 18. 
Mg2Si3O8 5H2O, 19.Kaolinite 
5
2
X
Si K
Fig. 3 2 SiK
Si K
K
Si
Si
, 2
Si O M
2 Si
Si O
Si SiO2 K
Si O Si K
K K K
Fig. 4 Si O
K Si O K
SiK P Al, Fe K X
AlK Fig. 5 Al
2
AlK Al
X
X
X NMR
0 0.2 0.4 0.6
-0.2
-0.1
0
0.1
Na2O GeO2
Na2O SiO2
Na2O P2O5
Mol fraction of  Na2O
C
he
m
ic
al
 s
hi
ft 
/e
V
 (r
ef
er
en
ce
 : 
A
l 2O
3)
Fig. 5  Al K chemical shift 2 % doped  
in Na2O-B2O3, Na2O-SiO2, Na2O-GeO2
and Na2O-P2O5 glass. (Reference:Al2O3)
6
2.3 放射線照射による着色現象[4]-[6]
F l l2
k
ig. 6
50 V 30 mA
1 106
Rad 2 eV
eV
Fig. 7 2
Fig. 8 
B2O3 3 4
3 30 mol%
4 Fig. 8
0 0.1 0.2 0.3 0.4
0
1
2
3
4
5
 Na2O-B2O3
 K2O-B2O3
Mole Fraction of Na2O or K2O
O
pt
ic
al
 a
bs
or
pt
io
n 
/ c
m
-1
Fig. 7 Intensity of alkali associated electron 
Center by X-ray irradiation  
Wave length / nm
Energy / eV
O
pt
ic
al
 a
bs
or
pt
io
n 
/c
m
-1
a
b
c
d
e
f
Fig. 6  Radiation induced optical spectra of  
Na2O-B2O3 glasses. a: 33 mol %, b: 30 %,c: 
25 %, d: 20 %, e: 15 %, f; 10 % Na2O
7
ー O ー B
O
O－Ｎa＋
O
ー O ー B
O
h
＋ Na＋ ＋ e
O
Na＋
B －O － B － O
O
O
O
O
O
B －O － B － O ＋ Na＋＋ e
O
O
h
（a） （b)
（c)
F
Fig. 8 a 2.10 eV 
1.98 eV 20
KCl
K2O-B2O3 X
3.7 eV
Cl2 KCl
Fig. 9 KCl
K2O
K2O 20mol %
Fig.7
X
KCl KCl
K2O
20 %
KCl
X Cl2
Cl2
KF KBr KI
3.90, 3.50 3.20 eV
Mol % of K2O
O
pt
ic
al
 a
bs
or
pt
io
n 
/ c
m
-1
Fig. 8 The structure of defect centers in sodium borate glasses. (a)  alkali associated 
electron center, (b) hole center associated with the non-bridging oxygen ion, c  Hole center 
associated with the tetrahedral coordinated boron atoms. 
Fig. 9 The composition dependence of the 
3.7 eV peak (Cl2  center) in K2O-B2O3-KCl 
glasses with 1 mol % KCl 
8
X
X
,
Fig.10
45 MeV
LINAC
,
1 Fig. 11
2
Fig. 12 
Na2O 7SiO2 5 s 77K X
s X-
１
２
３
４
５
６
７
８
９
１０１１
１２ １３
１４ １５ １６
Fig. 10 Schematic diagram of the pulse radiolysis system 
1. e lamp 2. slit 3. chopper  4. lamp  5. photodiode  6. LINAC (45 MeV)  7. sample 
8. Concrete wall  9. monochrometer  11. Photomultiplier  12. Linac control panell
13. Delay circuit  14. CRO  15. Digital memory  16. PC or X-Y recorder  
730 
nm
510 nm
0 400 0 400
time / μs time / μs
A
bs
or
ba
nc
e
Fig. 11 Typical pulse radiolysis curve for  
3Na2O-7SiO2 glass 
9
,
2.4 固体 MAS NMR による構造単位の見積もりと塩基度[7]-[10]
 X ,
MAS-NMR
Fig. 13
Qn
SiO2 Si O Si Si O
Si
SiO2
SiO2
Q4
Q3 Q2 Q1 Q0 Si ,NMR
Qn
Q4 Q3 Q2 Q1
SiO2 Fig.13
Q Li2O < Na2O < K2O
Li2O < Na2O < K2O X
0 10 20 30 40 50 60
0
20
40
60
80
100
Q1Q2Q3Q4
M2O / mol %
Q
n /
 %
Fig.13 Experimentally determined Qn 
distributions in Li ( ), Na( ) and K( )
silicate glasses as a function of mol% of Alkali 
oxide. 
A
bs
or
ba
nc
e
Energy / eV Energy / eV Energy / eV
Wave length / nm Wave length / nm Wave length / nm
3Na2O・7SiO2
3K2O・7SiO2
3Li2O・7SiO2
Fig. 12  Pulse irradiated absorption spectra of lithium-, sodium-, and potassium silicate 
glasses.  ―●― :  5μs， ―○― :  100 ms， ―― ： 1s after irradiation 
10
NMR
Q Q3 Q1
K2 [Q3] [Q1] / [Q2]2
K2 0.30(Li2O) 0.06(Na2O) 0.01(K2O)
Na2O P2O5
P NMR Qn 50 mol % 
Na2O P Q2 P2O5 SiO2
Na2O
SiO2 SiO4 ,SiO2
Fig. 14
X P2O5
210ppm SiO2
Si SiO2 P2O5
Na2O
SiO2 P2O5
Fig. 15 Na2O SiO2 P2O5 6 Si
SiO2 0.48
SiO2 SiO2 4
6
(MO SiO2 Al2O3 B2O3)
11B, 27Al, 29SiNMR M
M’2O
Fig. 16 0.188MO
0.673SiO2 0.077Al2O3 0.062B2O3 11B
NMR 11BNMR 
3
Fig 17 0.139MO 0.673SiO2 (0.188
)Al2O3 B2O3 Q3
-100 -200
Chemical shift /ppm
Si (Q6)→
Fig. 14 29Si NMR spectra of  
30Na2O SiO2 65[(1-x)P2O5 xB2O3]
glasses  
0.4 0.5 0.6
0
50
100
Optical Basicity
[S
iO
6]/
([S
iO
6]+
[Q
4])
   
  % SiO2) = 0.48
Fig. 15 The relation between fraction of 
six-coordinatred Si atom in 
Na2O-SiO2-P2O5 glasses and optical 
basicity 
11
Si(Q3) B(Q3)  Si(Q4) + B(Q4)
K = [Si(Q4)] [ B(Q4)] / [Si(Q3)] [B(Q3)]
K MgO (0.04 0.04) < CaO (0.3 0.1) < SrO (1.1 0.3) < BaO (4.0 0.4) < Na2O (8.0
3) < K2O (18 5) B2O3 B2O3 SiO2
B2O3
2.5 ガラス融体の酸塩基と酸化還元―清澄作用[11],[12]
Fig. 2) Na2O
K2O Na2O
BaO
SrO
CaO
MgO
% of Si(Q3)
%
 o
f B
(Q
4)
-20020
Chemical shift / ppm
M'=Na
Sr
Ba
M=Ca
In
te
ns
ity
Fig 16 11B NMR spectra of 0.188MO
0.673SiO2 0.077Al2O3 0.062B2O3
glasses 
Fig. 17 Relation between fractios of B(Q4)
and Si(Q4) in 0.139MO 0.673SiO2 (0.188
)Al2O3 B2O3 glasses 
12
Fig. 18
(1/2) O2 + 2 e = O2 Reference electrode
Sb5+ + 2 e = Sb3             Working electrode
2
Sb3  + (1/2) O2 = Sb5  + O2
Ag Pt
0
E = Eo' + (RT/2F) ln [Sb5+] / [Sb3+] (RT/4F) ln p(O2)
E1/2 = Eo' + (RT/4F) ln D(Sb3+) / D(Sb5+)
D
E1/2   (RT/2F) ln [Sb5+] / [Sb3+] (RT/4F) ln p(O2)
E1/2
Fig. 19 0.21 atm
(RT/4F) ln p(O2) 47 mV 45 mV
Fig. 20 16Na2O 10SiO2 74SiO2
0 500 1000 1500
-620
-600
-580
-560
-540
-5200 10 20 30
Pe
al
 p
ot
en
tia
l /
 m
V
Time / min
Time / hr
O2 (P(O2)=1atm)
Air(P(O2)=0.21atm)
45mV
T=1473K
Counter
electrode
Reference
electrode
Melt
Working 
electrode
Fig. 18 Schematic cell assembly for voltammetry 
Fig. 19 Variation of peak potential with 
oxygenpressure over the 16Na2O 10SiO2
74SiO2 glass 
13
Sb5 Sb3
0 V Sb3+ Sb5+
Sb3+
V
,
15 min    30 min    60 min   90 min 
Fig. 21 Fig. 22 75
[13]
1000 1200 1400 1600 1800
-100
0
100
200
300
800 1000 1200 1400
T/K
T/
E 1
/2
/m
V
Fig. 20 Relationship between E1/2 and 
temperature for 16Na2O 10SiO2 74SiO2
glass
Fig. 21 Schematic model of fining used 
 antimony ion as a refining reagent 
Fig. 22 The bubbles in glass : upper. no 
Sb,  lower, 01 g Sb in 100 g glass 
14
3. まとめ
Table 2
P2O5 Al2O3 B2O3 iO2 Al2O3
6
X Al NMR
Al2O3
Na2O
Al2O3 Na2O Al2O3 Na2O SiO2 B2O3
SiO2 B2O3 NMR
Table 1
Table 2  The strength of acids and their conjugated bases of various oxides [14]
        
P2O5  PO3 P2O5  Si2O52 Q3 = 2 SiO2 (Q4) + 2 PO3
Al2O3  AlO2
B2O3 B8O132 4 B2O3 +  Si2O52 Q3 =  2 SiO2 (Q4) + B8O132
WO3 WO42
B8O132 B4O72
SiO2 Si2O52   2 SiO2 (Q4)  Na2O = Si2O52 Q3  2 Na
PO3 P2O72
H H2O
Si2O52 SiO32   Si2O52 Q3  Na2O = SiO32 Q2  2 Na
B4O72 B2O54
CO2 CO32
P2O72 PO43
SiO32 Si2O76   2 SiO32 (Q2  Na2O = Si2O76 (Q1) 2 Na
Si2O76   SiO44   Si2O76 (Q1) 2 Na2O = 2 SiO44  (Q0) 2 Na
Fe2 FeO 
Mg2 MgO 
H2O  OH
Ca2 CaO
Na Na2O
15
[1]  T. Maekawa, T. Yokokawa and K. Niwa, “Solubility of Ag2O in Na2O-B2O3 Melts”, Bull. Chem. Soc. Japan, 
vol. 42, pp. 677-681, 1969 
[2]  T. Maekawa, N. Kikuchi, S. Sumita and T. Yokokawa, “X-Ray Fluorescence Spectroscopy of Binary 
Silicate Glasses”, Bull. Chem. Soc. Japan, vol. 51, pp. 780-782, 1978 
[3]  X 24
186-192 1985 
[4]  
92 398 404 1984 
[5]   
Vk 93 30-37 1985 
[6]  T. Maekawa, T. Yokokawa, S. Sawamura, M. Kitaichi and M. Katayama, “Pullse Radiolysis Studies of 
oxide Glasses”, J. Non-crystalline Solids, vol. 95&96, pp. 693-700, 1987 
[7]  H. Maekawa, T. Maekawa, K. Kawamura and T. Yokokawa, “The Structural groups of alkali silicate glasses 
determined from 29Si MAS-NMR”, J. Non-crystalline Solids, vol. 127, pp. 53-64, 1991 
[8]  H. Yamashita, H. Yoshino, K. Nagata, I. Yamaguchi, M. Ookawa and T. Maekawa, “NMR and Raman 
Studies of Na2O-P2O5-SiO2 Glasses Six-coordinated Si and Basicity ”, J. Ceramic Soc. Japan, vol. 106, 
pp. 539-544, 1998 
[9]  H. Yamashita, K. Inoue, Y. Nakajin, H. Inoue and T. Maekawa, ”Nuclear magnetic resonance studies of 
0.139MO(or M’2O) 0.673SiO2 (0.188 x)Al2O3 xB2O3 (M=Mg, Cs, Sr and Ba, M’=Na and K) glasses, 
J. Non-crystalline Solids, vol. 331, pp. 128-136, 2003 
[10]  T. Maekawa, “Chemical Reactions Occurred in Oxide Glasses and Their Melts and Evaluation by 
Acid-Base Concept : NMR Investigation of Multi-Component Silicate Glasses (Special Article, The 58Th
CerSJ Awards for Academic Achievements)”, J. Ceramic Soc. Japan, vol. 112, pp 467-471, 2004  
[11]  H. Yamashita, S. Yamaguchi, R. Nishimura and T. Maekawa, “Voltammetric Studies of Antimony Ions in 
Soda-lime- silica Glass Melts up to 1873K”, Analytical Science, vol. 17, pp. 45-50, 2001 
[12]  New Glass, vol. 21, no. 6, pp. 4-9, 2006 
[13]  Von E. Zschimmer and L. Ernyei, “Über die Läuterung von Natron-Kalk-Silikatglas durch 
Antimon(3)Oxyd, Sprechsaal, vol. 65, pp. 177-179, 1932 
[14]  1998 
     


Acid-Base and Redox Properties of Oxide Glasses and Their Melts : Spectroscopic Investigation for Glasses and Thermodynamics of the Melts

内海, あずさ

榊原, 正幸

佐野, 栄

世良, 耕一郎

川又, 明徳

訂　正
愛媛大学理学部紀要第 15 巻に掲載されました
榊原ほか論文 (p.17-26) の著者所属に以下の誤
りがありました． 訂正し， 深くお詫びいたします．
誤 ： 内海あずさ 1     榊原正幸 1
    佐野　栄 2    　 世良耕一郎 3
    川又明徳 4
     5 愛媛県立総合科学博物館
正 ： 内海あずさ 1     榊原正幸 1,2
    佐野　栄 3    　 世良耕一郎 4
    川又明徳 5
     5 愛媛県総合科学博物館
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