From:
Alfred Margaryan
“Ligands and
Modifiers in Vitreous Materials: Spectnoscopy of
condensed Systems”
Publisher: World Scientific,
___________________________________________________________________________________________________________________________
The use of glass hosts for
active elements in lasers and fiber optics has stimulated interest in new
vitreous materials, including fluorophosphates.
Sun [65-69] developed first a
composition of vitreous fluorophosphate systems on
the base metaphosphate aluminum and fluorides of
metal from the first and second group of the Periodic system. Optical constant
of glasses is nD=1.45-1.59, n=53-73.
Table 5.6 shows some
compositions of fluorophosphate glasses and optical
constants from the data of Sun [65-69].
Yahn [70-72] offered compositions of fluorophosphate
glasses with nD=1.45-1.58 and n=67-88 on the base metaphosphate
and pyrophosphate alkaline and earth alkaline metals. Some of those
compositions are presented in Table 5.7.
Table 5.6
Compositions of Fluorophosphate Glasses (in mol%)
(from [65-69] )
|
Components |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
|
BaF2 |
61.1 |
41.8 |
19.7 |
- |
- |
42 |
- |
45 |
|
CaF2 |
9.8 |
- |
25.1 |
- |
- |
- |
- |
- |
|
ZnF2 |
- |
- |
- |
- |
- |
- |
- |
- |
|
Al(PO3)3 |
29.1 |
18.6 |
19.7 |
17.3 |
24.2 |
25 |
18.7 |
25 |
|
ThF4 |
- |
39.6 |
- |
- |
- |
- |
- |
- |
LiF
|
- |
- |
35.5 |
82.7 |
- |
- |
77.0 |
- |
|
NaF |
- |
- |
- |
- |
59.6 |
- |
- |
- |
|
PbO |
- |
- |
- |
- |
16.2 |
- |
- |
- |
|
PbF2 |
- |
- |
- |
- |
- |
33 |
- |
- |
|
TiO2 |
- |
- |
- |
- |
- |
- |
4.3 |
- |
|
CdF2 |
- |
- |
- |
- |
- |
- |
- |
30 |
|
nD n |
1.5654 70.2 |
1.5919 69.9 |
1.5305 73.0 |
1.4573 73.9 |
1.5138 54.8 |
- - |
1.4820 53.1 |
1.5959 62.8 |
Table 5.7
Compositions of Fluorophosphate Glasses (in mol %) (from
[70-72] ).
|
Components |
1
|
2 |
3 |
4 |
5 |
|
MgF2 |
20 |
18 |
13 |
13 |
17 |
|
CaF2 |
19 |
18 |
13 |
23 |
17 |
|
SrF2 |
- |
18 |
20 |
14 |
18 |
|
BaF2 |
19 |
18 |
19 |
14 |
18 |
|
LaF3 |
1 |
- |
1 |
1 |
1 |
|
AlF3 |
26 |
18 |
22 |
25 |
22 |
|
NaPO3 |
5 |
10 |
- |
- |
8.0 |
|
LiPO3 |
- |
- |
12 |
- |
- |
|
Mg(PO3)2 |
- |
- |
- |
10 |
- |
nD
n |
1.4529 88.8 |
1.4614 87.23 |
1.4749 86.3 |
1.4704 86.2 |
1.4570 84.8 |
Several authors [73-76]
studied domains of glass forming and some physicochemical and optical
properties in the Al(PO3)3-BaF2-RF2(R-Mg,Ca,Sr) systems. Glass forming range decreases with
increasing ion radii of bivalence cations. Barium
fluoride is an essential component in these glass systems. IR spectroscopic
investigation of the glasses shows that structural lattices of those glasses
have phosphate, fluoride and fluorophosphate groups
[76].
According to Murthy [77, 78]
structure of glass system NaPO3-NaF has a chain texture with ortho and pyrophosphate groups, and also the presence of monofluorophosphate group – (PO3F)2-.
Laidtorp et al. [79-81] investigated the ability of glass
formation and physicochemical and spectroscopic properties of fluorophosphate glasses on barium monofluorophosphate (BaPO3F) base. Optical
constants of those glasses was
nD=1.46-1.62,
n=62-88.
Tetsuro and Seiichi [83] created stable fuorophosphate
optical glass in the system:
B2O3-P2O5-MF
(M-Li, Na, K) and B2O3-P2O5-RF2
(R-Mg, Ba, Ca).
Vogel and Gerth
[84] recommended a method of creating fluorophosphate
optical glasses with nD=1.45-1.53, n=55-80. These glasses were synthesized in systems
where RF=16-34, MeSiF6=5-54, Al(PO3)3=30-63(wt%),
R-Li, Na, K; Me-Mg, Ca, Sr, Ba,
Cd, Zn, Pb.
Auzel and Morin [85] fabricated a composition fluorophosphate glass for laser use, doped with erbium and
ytterbium, where BaF2=33.41, AlF3=21.90, CaF2=14.87,
MgF2=12.50, NaPO4=17.32
(in wt%).
Vrtanessian et al.[86, 87] studied the
domain of glass formation and physicochemical properties of boron containing fluorophosphate glasses in BaPO3F-B2O3-RxOy,
where R-Mg, Ca, Sr, Ba, Al.
Ability of glass formation increases with increasing strength of the modifiers
field.
Wassilac et al.[88-90] investigated
properties, structure and spectroscopy of fluorophosphate
glasses in Ba(PO3)2-MgF2-0.4AlF3
. 0.6CaF2. Glasses was doped with Nd(III),
Eu(III), Ho(III), Er(III)
and Yb(III). They established correlation between
shift of spectral lines and concentration of fluorides in the glass. When
increasing contents of fluorides in fluorophosphate
glass accordingly increases degree of ionicity
between dopant-ligand bond.
Pogosyan et al.[91, 92] studied glass
formation, properties and structure of alkaline-fluorophosphate
glasses in the NaPO3-LiF-(0.4AlF3 . 0.6CaF2) and (0.3LiF . 0.7NaPO3)-AlF3-MeF2
(Me-Mg, Ca) systems.
Domain of glass formation in pseudobinary systems Ba(PO3)2-RF2 increases in the
order BaF2(25)®SrF2(35)®CaF2(50)®MgF2(70mol%) [93]. Introduction of RF2 in
Ba(PO3)2 decreases the intensity of
characteristic bands of metaphosphates (1260-1240cm-1)
in the IR spectra, but increases spectral bands from pyrophosphate groups
(1145-1110cm-1 and 930-905cm-1). Increasing the concentration of RF2
assist formation of tetrahedra [PO3F]
[93].
Urusovskaya et al.[94] have done EPR
investigation of Al(PO3)3-RF (R-Li, Na, K) glasses, doped
with Mn(II) and Co(II). Established
data of nature of chemical bonds realizing in alumofluorophosphate
glasses. Large lasing effects were obtained from the base neodimium fluorophosphate glasses
[95].
Petrovski [96] showed the possibility of creating fluorophosphate glasses with monofluorophosphate
barium (BaPO3F) only 8mol%, other
components are fluorides alkaline earth and rare earth elements. Refractive
index of this glass is nD=1.43658,
coefficient dispersion n=95.8.
Margaryan et al.[97-105] studied
glasses in ternary fluorophosphate systems: P2O5-LaF3-RF2
(R-Mg, Ba), Ba(PO3)2-LaF3-RF2,
Ba(PO3)2-YF3-RF2,
Ba(PO3)2-Al(PO3)3-RF2
(R-Mg, Ca, Sr, Ba). The
domain of glass formation for glass system P2O5-LaF3-MgF2
is P2O5=40-100, LaF3=0-25, MgF2=0-60mol%,
for P2O5-LaF3-BaF2 is P2O5=50-100,
LaF3=0-25, BaF2=0-50mol%.
The IR spectra of the glasses
contain characteristic bands related to alkaline metaphosphates
[106], which are observed in the spectral range 1325-1250cm-1,
according to P-O bond in (PO3)n1- anion [99,
100]. Presence of the bands in 760-730cm-1 will be carry to P-O-P
vibration of circular phosphates or P-F bonds in monofluorophosphate
anion [PO3F]2-. 1080
and 500cm-1 bands according to fundamental vibration of [PO4]3-
molecules [99]. Fluorophosphate type of glasses in P2O5-LaF3-RF2
consist from (PO3)n1-,
[PO3F]2-, [PO4]3- structural groups
[99, 100]. Figure 5.22 presents the
domain of glass formation for Ba(PO3)2-LaF3-RF2
and Ba(PO3)2-YF3-RF2
systems [102].
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Figure 5.22: Boundaries of
glass formation (from [102]).
Limits of glass formation
increase with decreasing of ion radii of alkaline earth cations.
Yttrium containing systems
have a wide limits of glass formation. Glasses in Ba(PO3)2-YF3-BaF2
are formed in Ba(PO3)2=35-100,
YF3=0-60, BaF2=0-25mol%. Glasses in Ba(PO3)2-YF3-MgF2
are formed in Ba(PO3)2=25-100,
YF3=0-60, MgF2=0-70mol%.
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Figure 5.23: IR spectra of
glasses of the system Ba(PO2)3 – LaF3 – RF2 (from
[102]).
(1) glass forming Ba(PO3)2, (2) 80Ba(PO3)2
. 20LaF3, (3) 80Ba(PO3)2 . 20BaF2,
(4) 80Ba(PO3)2 . 10LaF3 . 10BaF2, (5) 80Ba(PO3)2 . 20SrF2,
(6) 80Ba(PO3)2 .
20CaF2, (7) 60Ba(PO3)2
. 40CaF2, (8) 80Ba(PO3)2
. 10LaF3 . 10CaF2,
(9) 60Ba(PO3)2
. 10LaF3 . 30CaF2,
(10) 50Ba(PO3)2 . 10LaF3 . 40CaF2,
(11) 80Ba(PO3)2
. 20MgF2, (12) 60Ba(PO3)2
. 40MgF2, (13) 40Ba(PO3)2
. 60MgF2, (14) 80Ba(PO3)2
. 10LaF3 . 10MgF2,
(15) 60Ba(PO3)2 . 10LaF3 . 30MgF2,
Figure 5.23 and 5.24
illustrate the IR spectra of Ba(PO3)2-LaF3-RF2
and Ba(PO3)2-YF3-RF2
glasses [102]. IR spectra of glass forming metaphosphate
barium-Ba(PO3)2
are characterized by the appearance of the spectral bands on the 1265, 1150,
1090, 1000, 885, 775, 520 and 475cm-1 [107].
Born [108] and Thilo [109] indicated, that the structure of metaphosphate anions depend on the ion sizes of respective cations. Small and big cations
form polyphosphates with anions chain. Cations of
average size form metaphosphates with circular
anions.
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Figure 5.24: IR spectra of glasses of the system Ba(PO2)3
– YF3 – RF2 (from [102]).
(1) glass forming Ba(PO3)2, (2) 80Ba(PO3)2
. 20BaF3, (3) 80Ba(PO3)2 . 20YF3,
(4) 60Ba(PO3)2 . 40YF3,
(5) 60Ba(PO3)2 . 20YF3 . 20BaF2,
(6) 60Ba(PO3)2
. 20YF2 . 20SrF2,
(7) 50Ba(PO3)2 . 20YF3 . 30SrF2,
(8) 60Ba(PO3)2
. 40CaF2, (9) 60Ba(PO3)2
. 20YF3 . 20CaF2,
(10) 50Ba(PO3)2
. 20YF3 . 30CaF2,
(11) 60Ba(PO3)2 .
40MgF2,
(12) 40Ba(PO3)2
. 60MgF2, (13) 60Ba(PO3)2
. 20YF3 . 20MgF2,
(14) 50Ba(PO3)2
. 20YF3 . 30MgF2,
(15) 30Ba(PO3)2 . 20YF3 . 50MgF2.
Petrovski et al.[110, 111] established
that in the crystalline form of barium metaphosphate
predominate tetrametaphosphate circular groups type
of (P4O12)4-. The crystalline form transforms
in the glass forming state to Ba(PO3)2 accompanied by breaking of tetrametaphosphate circles with formation of chains of (PO3)n1-
[107]. Introducing fluorides of alkaline earth elements in glass forming Ba(PO3)2
preserves the tetraphosphate radical (P4O12)4-
[110].
Figure 5.23, and 5.24
illustrate, that introduction of any of the alkaline earth fluorides, LaF3
and YF3 in glass forming Ba(PO3)2 leads to decreasing of the
bands intensity in IR spectra of metaphosphate
anions. In the presence of RF2 and RF3 in 30-50mol% and
above observed that IR bands disappear, characteristic of glass forming Ba(PO3)2.
When concentration of fluorides increasing in glass forming Ba(PO3)2
on IR spectra displayed intense bands of
absorption which is described by the presence of pyrophosphate groups in
vibration range of 1145-1110cm-1 (nas PO3)
and 930-905cm-1 ( nas P-O-P)
(Figure 5.23 and Figure 5.24). Glass 60Ba(PO3)2
. 40CaF2
(curve 7, Figure 5.23), basically formed pyrophosphate groups of structure in
the range of frequency 560, 690, 910cm-1 (d-Ba2P2O7).
When the content of fluorides
is 40-50mol% (curves 9, 10, Figure 5.23) intensity of corresponding bands
increases respectively for pyrophosphate groups with 560, 930-910, 1140-1110cm-1
and tetrametaphosphate (740-730cm-1).
Curves 11-15 (Figure 5.23) presents vibration frequency of glasses Ba(PO3)2-LaF3-MgF2.
When the concentration of fluorides is above 30mol% (curves 12, 13, 15) basic
structural groups formed tetrametaphosphates and
pyrophosphates. When MgF2 is 40 and 60mol% (curves 12 and 13)
spectral band in 755-735cm-1 interval can be ascribed bonds P-F in
the monofluorophosphate anion (PO3F)2-. Probably anions of (PO3F)2- are formed in fluorophosphate
glasses in the presence of the high concentration of fluorides.
IR spectra of the glass
system Ba(PO3)2-YF3-RF2
(Figure 5.24) present analogous spectra to glasses of Ba(PO3)2-LaF3-RF2
(Figure5.23). Glasses in the system Ba(PO3)2-YF3-MgF2,
can have concentration of fluorides up to 70mol%. High content of fluorides
(more than 40mol%) assist in the formation of the
bonds between nuclei of fluorine and phosphorus in minofluorophosphate
tetrahedra (PO3F)2-.
Curves 11-15 (Figure 5.24)
show IR spectra of yttriumcontaining fluorophosphate glasses with MgF2 20-60mol%,
where this common content of fluoride is 40-70mol%. IR spectra of glasses
change according to the content of fluorides. MgF2 has a special
role in formation of structure of fluorophosphate and
fluoride glasses. Between interval of frequencies 760-755cm-1 on the
curves 11, 12 and 15 (Figure 5.24) (MgF2 to 40-60mol%)
providing intense bands of the bonds P-F in (PO3F)2-
anion. These type of glasses form on the base of the pyrophosphate (930-900cm-1)
and monofluorophosphate groups of structure. Glass
formation in the Ba(PO3)2-LaF3-RF2
and Ba(PO3)2-YF3-RF2
systems are realized by coexistence of (PO3)n1-,
(P2O7)4-, (P4O12)4-,
(PO3F )2- and fluoride groups, specially [MgF4]2-.
Figure 5.25 shows boundaries
of glass formation of fluorophosphate glasses with
two glass former metaphosphates (barium and aluminum)
and fluorides of alkaline earth metals [104]. Wide domain of
glass forming fluorophosphates form in the line Ba®Sr®Ca®Mg.
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Figure 5.25: Boundaries of
glass formation (from [104]).
An exception is Ba(PO3)2-Al(PO3)3-BaF2,
where there are two separate ranges of glass formation. Glasses in range I
formed at Ba(PO3)2=10-80, Al(PO3)3=10-80,
BaF2=10-20mol%, glasses in range II at Ba(PO3)2=10-40,
Al(PO3)3=10-20, BaF2=50-70mol%.
The domain of glass formation
in the Ba(PO3)2-Al(PO3)3-RF2
systems is according to the follow limits: Ba(PO3)2=0-100,
Al(PO3)3=0-100, MgF2=0-70, CaF2=0-50,
SrF2=0-35, BaF2=0-25mol%.
Figure 5.26 presents IR
spectra of glasses Ba(PO3)2-Al(PO3)3-RF2
systems [104]. IR spectra of glasses present a superposition of bands at glass
forming Ba(PO3)2
and Al(PO3)3. Intensity of characteristic bands of IR
spectra depend on the concentration of Ba(PO3)2 and Al(PO3)3
in developed glasses.
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Figure 5.26: IR spectra of
glass of the system Ba(PO3)2 – Al(PO3)3
– RF2 (from [104]).
(1) glass forming Ba(PO3)2, (2) glass forming Al(PO3)3,
(3) 20Al(PO3)3 . 80Ba(PO3)2,
(4) 50Ba(PO3)2 . 50Al(PO3)3,
(5) 80Al(PO3)3 . 20Ba(PO3)2,
(6) 80Al(PO3)3
. 20BaF2, (7) 80Ba(PO3)2
. 20BaF2, (8) 40Al(PO3)3
. 40Ba(PO3)2 . 20BaF2,
(9) 50Al(PO3)3 . 30Ba(PO3)2 . 20BaF2,
(10) 60Al(PO3)3 . 20Ba(PO3)2 . 20BaF2,
(11) 10Al(PO3)3 . 40Ba(PO3)2 . 50BaF2,
(12) 10Al(PO3)3 . 30Ba(PO3)2 . . 60BaF2,
(13) 10Al(PO3)3 . 20Ba(PO3)2 . 70BaF2,
(14) 20Al(PO3)3 . 10Ba(PO3)2 . 70BaF2,
(15) 20Al(PO3)3 . 60Ba(PO3)2 . 20BaF2,
(16) 30Al(PO3)3 . 50Ba(PO3)2 . 20BaF2,
(17) 80Al(PO3)3 .
20SrF2, (18) 80Ba(PO3)2 . 20SrF2, (19) 10Al(PO3)3
. . 70Ba(PO3)2 . 20SrF2,
(20) 70Al(PO3)3 . 10Ba(PO3)2 . 20SrF2,
(21) 80Al(PO3)3 .
20SrF2, (22) 80Ba(PO3)2 . 20CaF2,
(23) 10Al(PO3)3 . 70Ba(PO3)2 . 20CaF2,
(24) 70Al(PO3)3
. 10Ba(PO3)2 . 20CaF2,
(25) 80Al(PO3)3 . 20MgF2,
(26) 80Ba(PO3)2
. 20MgF2, (27) 10Al(PO3)3
. 70Ba(PO3)2 . 20MgF2,
(28) 70Al(PO3)3
. 10Ba(PO3)2 . 20MgF2,
With increasing contents of metaphosphates, IR spectra are displace to the side of the
frequencies of vibrations of Ba(PO3)2 and Al(PO3)3
respectively: curve 3-20Al(PO3)3 . 80Ba(PO3)2,
curve 4 – 50Al(PO3)3 . 50Ba(PO3)2
and curve 5 – 80Al(PO3)3 . 20Ba(PO3)2
(Figure 5.26).
Introduction in glass
fluorides of alkaline earth element causes decreasing of intensity of basic
bands of glass forming Al(PO3)3 and Ba(PO3)2
and new bands of absorption appear, which belong to pyrophosphate, monofluorophosphate and tetrametaphosphate
groups.
Special interest are glasses
of Al(PO3)3-Ba(PO3)2-BaF2.
Glasses with BaF2 at 50 to 70mol% (curves 11-14, Figure 5.26) at
760-745cm-1 show formation of tetrahedral anions of (PO3F)2-.
Interval vibration 940-870cm-1
(nas P-O-P in d Ba2P2O7) describes
formation of pyrophosphate groups (P2O7)4-
(curves 8-16, Figure 5.26) in structure of glass. Thus fluorophosphate
glasses Al(PO3)3-Ba(PO3)2-BaF2
are formed from anion type of elements of the structure (PO3F)2-,
(P2O7)4-, (P4O12)4 and
(PO3)n1-. Glasses Al(PO3)3-Ba(PO3)2-(Sr, Ca, Mg)F2 (curves 17-28, Figure 5.26) which
contain fluorides of alkaline earth elements up to 20mol% glass formation is
realized by (PO3)n1- and (P2O7)4-
structural groups.
Margaryan et al. [105, 112, 113] provided
investigations of luminescence, electron absorption and EPR spectra of fluorophosphate glasses doped with Mn(II).
Spectral characteristics of Mn(II)
for different types of fluorophosphate systems very
close to each other (luminescence spectra Figure 2.8 and Figure 2.10, absorption
spectra Figures 3.9; 3.10 and 3.11).
Definite interest presents
spectroscopic investigations of Mn(II) in Ba(PO3)2-PbF2(BiF3)
and Ba(PO3)2-YF3-PbF2(BiF3)
glasses [114]. The glass composition investigated (in mol%) were: 45Ba(PO3)2
. 55PbF2(BiF3),
50Ba(PO3)2 .
20YF3 . 30PbF2(BiF3).
The luminescence spectra of glasses, doped with Mn(II), are shown in Figure
5.27. Increasing the concentration of dopant,
shifts the broad band spectrum toward a longer wavelength region.
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Figure 5.27: Luminescence
spectra of Mn(II) in glass with composition(mol%):
50Ba(PO3)2 . 20YF3 . 30PbF2 (curves 1, 2
and 3), and
50Ba(PO3)2 . 20YF3 . 30BiF3 (curves 4, 5
and 6) (from [114])
The colour
of the luminescence changes from yellow to dark red. The peak position is approximately
610nm when the MnF2 concentration is 0.5wt% and 720nm when its
concentration is 15wt%.
Changes in
the chemical bond between dopant and ligands is the
main factor affecting the luminescence [115, 116]. Phosphorus in fluorophosphate and phosphate glasses bonds more strongly
to oxygen or fluorine than the silicon in silicate glasses. Phosphorus has a
larger nuclear charge and forms five covalent bonds as compared to four for
silicon:
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In fluorophosphate
glasses, in which F-Mn-F, or
F-Mn-O-bonds occur, the degree of covalence lies
between that of phosphate and fluoroberyllate glasses
[117]. Absorption spectra of the glasses
are shown in Figure 5.28. The absorption band corresponding to the 6A1g(S)®4Eg(G)
transition is the most intense. The position of the maximum for investigated
glasses is 24320cm-1. The second most intense band to the 6A1g(S)
® 4Eg(D)
transition at 28700 cm-1.
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Figure 5.28: Absorption
spectra of Mn(II) in glass with composition(mol%):
50Ba(PO3)2 . 20YF3 . 30BiF3 (curves 1
and 2), and
50Ba(PO3)2 . 20YF3 . 30PbF2
(curves 3 and 4) (from [114]).
Fluorophosphate glasses are close to the phosphate glasses in degree
of covalence of the dopant-ligand bond. This is also confirmed by comparison of the Racha coefficient, B, for these glasses. The magnitude of B decreases with decrease in
size of the effective nuclear charge for free ions[118]. A decrease in the B value can be used to
infer an increase in the degree of covalency of Mn(II)
with the surrounding ligands [119]. The coefficient B can be calculated from the
Tanabe-Sugano equation [120]. In bismuth
and lead containing fluorophosphate glasses B=632 and
634 cm-1 respectively.
For fluoroberyllate,
phosphate and silicate glasses, the parameter B is approximately 700, 620 and
600, respectively [118].
The bands 4Eg(G)
and 4Eg(D) (Figure 5.28) do not depend on the strength of the
field. In the spectrum, there is a 4T1g(G) band, whose position depends
on the strength of the ligand field. This makes it possible to compare the
strength of the ligand fields in glasses with various
compositions for dopant ions with dn electrons.
According to Figure 5.28, the
energy difference between the terms 4Eg(G)
and 4T1g(G) for the fluorophosphate
glasses is 4320cm-1. For fluoroberyllate, phosphate and silicate glasses the value
are 4070, 4700 and 8250cm-1, respectively [118]. The strength of the ligand
field increases in the order fluoroberyllate, fluorophosphate, phosphate and silicate of the glass
series.
From EPR spectra was found the
hyperfine splitting(hfs) for Mn(II)
in glasses: 45Ba(PO3)2
. 55BiF3 and 45Ba(PO3)2
. 55PbF2, where A=94.33 and 92.12 Oe respectively. As
the concentration of Mn(II) increases, the width of the hfs lines increases, due to
spin-spin coupling between adjacent manganese ions (Figure 5.29).
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Figure 5.29: EPR spectra
of Mn(II)
in the glass(mol%) 45P2O5 . 55PbF2
at Mn(II): (1) 0.05, (2) 0.1, (3) 0.5, (4) 1.0, (5)
2.0wt% (from [114]).
The character of the bond,
which exists between the ligand-glass forming agent
and ligand-dopant, plays an important role. The hfs for Mn(II) is directly proportional to the number of ionic bonds
in the ligand-dopant series [20, 117, 118].
In the present time one of
the hot and actual problem is immobilization of
radioactive waste obtained from reprocessing irradiated nuclear fuel. Vitrification has
been identified as one of the most viable waste treatment alternative for
nuclear waste disposal. Currently, the
most popular glass compositions being selected for vitrification
are the borosilicate family of glasses and soda-lime-silicate variety
[121-127].
The
One option being studied is
to immobilize plutonium in a solid waste form, such as glass, and place it in a
deep, underground repository.
Now one of important problem
of vitrification of radioactive waste is a
development and investigation of the new effective composition of glasses,
which is able to absorb in the maximum level of nuclear irradiation and keep
for a long time safely the nuclear waste.
For this purpose, fluorophosphate type of
glasses have some advantage, containing fluorine and oxides dn
and ¦n elements, having a high radioactive resistance, owing
to high electronegativity of fluorine and reverse
change of valency of dn
and ¦n elements. On
the other hand high absorption of nuclear irradiation provided by existence of
lead fluorine in the vitreous fluorophosphate
systems.
The Environmental Protection
Agency (EPA) has declared vitrification the best
demonstrated available technology for high-level radioactive waste.