Professional Documents
Culture Documents
A Review On Immobilization of Phosphate Containing High Level Nuclear Wastes Within Glass Matrix
A Review On Immobilization of Phosphate Containing High Level Nuclear Wastes Within Glass Matrix
Review
h i g h l i g h t s
Technical review.
High level nuclear waste immobilization within phosphate glasses.
Integration of data from laboratory scale experiments, plant scale observations and natural rock information.
a r t i c l e
i n f o
Article history:
Received 10 April 2012
Received in revised form 12 July 2012
Accepted 18 July 2012
Available online 27 July 2012
Keywords:
High level nuclear waste
Immobilization
Phosphate glass
Review
a b s t r a c t
Immobilization of phosphate containing high level nuclear wastes within commonly used silicate glasses
is difcult due to restricted solubility of P2 O5 within such melts and its tendency to promote crystallization. The situation becomes more adverse when sulfate, chromate, etc. are also present within the waste.
To solve this problem waste developers have carried out signicant laboratory scale research works in
various phosphate based glass systems and successfully identied few formulations which apparently
look very promising as they are chemically durable, thermally stable and can be processed at moderate
temperatures. However, in the absence of required plant scale manufacturing experiences it is not possible to replace existing silicate based vitrication processes by the phosphate based ones. A review on
phosphate glass based wasteforms is presented here.
2012 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
5.
6.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Generation of phosphate rich HLW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Bismuth process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
PUREX process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
P2 O5 -HLWs storage as neutralized solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
P2 O5 -HLWs storage as calcined powder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Phosphate in silicate melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Lessons learnt from natural melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Difculties associated with phase separations within HLW loaded silicate melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Networking within phosphate melt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Immobilization of phosphate containing HLW within glass matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Future challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
18
20
20
20
20
21
21
21
21
22
23
25
26
26
18
1. Introduction
Eco-friendly and proliferation resistant management of spent
fuels is one of the most sensitive issues in the world today. Options
available at the back-end of nuclear fuel cycles are either
(i) direct disposal of spent fuel within suitable deep geological
repositories (better known as open fuel cycle), or
(ii) reprocessing it to extract valuables, followed by immobilizing
the process generated nuclear high level liquid wastes (HLWs)
within suitable inert matrice(s) for its interim storage and
disposal inside deep geological repositories (better known as
closed fuel cycle). Reaserch is also being pursued to segregate
and separately irradiate long lived minor actinides and ssion
products within critical and subcritical reactors to convert them
into shorter lived radionuclides (partitioning and transmutation; advanced fuel cycle; Fig. 1).
Recently, closed fuel cycle option has gained more importance
as it is environment friendly and economical [1]. In a simplied way, reprocessing begins with dismantling of water cooled
spent fuel bundles into pins and separating irradiated pellets from
Zircaloy (ZrSn alloys)/Al/stainless steel (FeCrNi alloys) clads
(protective metal jacket surrounding the fuel pellets) through
chopping (mostly by mechanical shearing) and dissolving the
small slices within concentrated acids (Fig. 2). The resultant solutions so obtained are highly hazardous as they contain various
Fig. 1. Schematic diagram showing basic differences between open and closed (advanced) nuclear fuel cycles.
Cooled
spent fuel
Shearing
19
U storage/
disposal
U oxide
U nitrate
solution
Chopping and
dissolution
Product
conversion
Reprocessing
Compaction/
Alloy formation
Vitrification
Pu nitrate
solution
MOX fuel
fabrication
Pu oxide
Product
conversion
Fig. 2. Schematic diagram showing major steps in the back-end part of closed nuclear fuel cycles.
on long time scale the wastes need to be immobilized within appropriate inert host matrices (wasteform), stored and disposed off
extremely carefully within suitable deep geological repositories so
as to isolate them from biosphere for as many as 104 106 years.
For conditioning of the HLWs, various amorphous (borosilicate
and aluminosilicate glasses), crystalline (synthetic rock SYNROC, titanate ceramics, phosphate ceramics (monazite, apatite and
related phases), calcines, alloys, etc.) and crypto-crystalline (glass
ceramics based on sphene, zirconolite, monazite, zircon, etc.) matrices [1224] have been proposed but the nal selection of wasteform
materials depends on several scientic and technological merits
and demerits associated with HLW compositions [25,26], product
durability factors, processing constraints [2733], service condition
demands [34,35], etc. Thus identication of a suitable wasteform
for any given HLW is a difcult task, and too much of expectations
in terms of its long term performance within geological repository
make the selection procedure even tougher. It is argued that the
environment within deep geological repository (constructed at a
depth of 5001000 m from the surface) is expected to be harsh due
to simultaneous interplay between (i) thermal eld, (ii) thermomechanical eld, (iii) biological eld, (iv) hydrological eld, (v)
chemical eld and (vi) radiation eld [36].
Table 1
Radionuclides commonly found within spent nuclear fuel.
Major actinides
234
Minor actinides
237
Np, 239 Np
Am, 242 Am, 243 Am
242
Cm, 243 Cm, 244 Cm, 245 Cm, 246 Cm
241
Fission materials
79
Activation products
Se, 85 Kr, 87 Rb, 89 Sr, 90 Sr, 93 Zr, 95 Zr, 95 Nb 99 Tc, 107 Pd, 115 In, 126 Sn, 129 I, 131 I 135 Cs, 137 Cs, 141 Ce, 142 Ce, 144 Ce, 144 Pr 144 Nd, 147 Sm, 147 Pm, 148 Sm,
149
Sm, 151 Sm, 133 Xe, 140 Ba, 134 Te, 93 Mo, 106 Ru, 106 Rh, 107 Pd, 140 La, 154 Eu
H, 10 Be, 14 C, 24 Na, 36 Cl, 39 Ar, 55 Fe, 59 Ni, 60 Co, 63 Ni, 93 Mo, 93m Nb, 94 Nb, 99 Tc, 108m Ag, 113m Cd, 121m Sn, 205 Pb, 210 Po
20
T1/2
Isotope
T1/2
Isotope
T1/2
95
65 days
57 min
8 days
40 h
95
Nb
Rh
134
Te
141
Ce
39 days
30 s
42 min
32 days
90
Sr
Ce
241
Am
60
Co
29
1.3
440
5.27
239
24,000
5730
76,000
20,300
Zr
Rh
133
Xe
140
La
103
1.7 107
7300
269
4000
106
144
Pu
C
59
Ni
94
Nb
14
In this process, decladded spent fuels were dissolved within concentrated HNO3 solutions containing Binitrate and H3 PO4 so as
to precipitate Pu4+ together with Biphosphate. The precipitates
were then centrifuged and dissolved in HNO3 , to which KMnO4
was added to convert Pu4+ to PuO2 2+ and kept it in solution while
allowing Biphosphate to precipitate out. In subsequent stages,
Pu was precipitated using ferrous sulfate (FeSO4 ), ferrous sulfamate [Fe(SO3 NH2 )2 ], sulfamic acid (HSO3 NH2 ), etc. while ensuring
formation of uranyl sulfate [UO2 (SO4 )2 2 ] such that U did not
coprecipitate with Pu. The precipitates were separated from ssion
products and sulfate containing solution through centrifugation,
and were subjected to decontamination in order to reduce overall
-activity; treated with Nabismuthate, H3 PO4 , HNO3 , HF, lanthanum salts, NaOH, oxalic acid, H2 SO4 , (NH4 )2 SO4 , etc. to nally
obtain Pu in the form of solid PuLa oxide. From this mixed oxide,
metallic Pu was derived via Punitrate formation. P2 O5 -HLWs generated at different stages were transferred to underground storage
tanks [42].
2.2. PUREX process
Although Bi-process was efcient enough to extract Pu in pure
form but it could not extract useful U, and also the volume of waste
generated was huge due to repetition of precipitation cycles. This
led to adaptation of continuous PUREX (Plutonium Uranium Redox
Extraction) solvent extraction process in plant scale where tributyl
phosphate (TBP; saturated in hydrocarbon (e.g. kerosene, etc.)) was
employed to coextract Pu and U from HLWs generated after dissolution of oxide-, carbide-, nitride-based spent fuels [40]. In this
process, chopped fuel pins were dissolved in concentrated HNO3
solution from which U (UO2 2+ ) and Pu (Pu4+ ) were coextracted
and subsequently separated by reducing Pu4+ to Pu3+ (either by
ferrous sulfamate or by hydroxylamine) while keeping UO2 2+ in
solvent phase. P2 O5 -HLWs obtained at the end of the process were
transferred to underground tanks.
2.3. P2 O5 -HLWs storage as neutralized solutions
Storage of P2 O5 -HLWs within steel tanks for decades led to
various physicochemical changes including (i) thermal and radiolytic breakdown of organic/inorganic compounds, (ii) generation
of hydrogen and other gases, (iii) release of large amounts of
heat due to interaction between ferrocyanides and nitrates, etc.
To avoid unwanted corrosion of storage tanks, the acidic liquids are now being neutralized with NaOH. However, ageing of
these HLWs together with addition of fresh waste batches, and
occasional evaporation to adjust HLW concentrations and volume, lead to segregation of the mass in the form of supernate
liquids, saltcakes and insoluble sludges ([42], Fig. 4). During the
course of evaporation, soluble Na salts present within supernate
liquids (e.g. nitrate, nitrite, aluminate, hydroxide, etc. [43]) get
crystallized out in the form of salt cake, which is dominantly
NaNO3 mixed with Na7 F(PO4 )2 19H2 O, Na3 FSO4 , Na2 C2 O4 , NaF,
Supernate liquid
Na salts (nitrate, nitrite, aluminate, hydroxide)
Salt cakes
Na -nitrate + chloride, fluoride, phosphate, sulphate
Sludge
ejkaite, clarkeite, nitratine, goethite, maghemite, amorphous
solids (Na, Al, P, O and C), spinels, quartz, Na-Al silicates
Fig. 4. Schematic diagram (not to scale) showing possible modes of compositional
variations within high-level waste storage tanks.
Na3 AlF6 , etc. [44]. Radioactivity present within supernate solution and salt cake is essentially due to the presence of Cs, Tc and
limited amount of Sr and transuranic elements. The sludge, on
the other hand is much more hazardous as it retains most of the
radionuclides present within HLW (excepting Cs) and essentially
constituted of Cejkaite
(Na4 (UO2 )(CO3 )3 ). Apart from this, presence of clarkeite (Na[(UO2 )O(OH)](H2 O)01 ), nitratine (NaNO3 ),
goethite [-FeO(OH)], magnetite (-Fe2 O3 ), amorphous solids (Na,
Al, P, O and C), (Fe, Cr, and Ni) oxides, SiO2 , Na Al silicates,
etc. have also been reported [45]. Thus, supernate liquid and salt
cakes together constitute low activity waste (LAW) and whereas
sludge constitute high level waste (HLW). The radioactive components present within LAW are recovered through isotopic dilution,
transuranic precipitation, ultraltration and ion-exchange process
and are added to HLW fraction [46].
2.4. P2 O5 -HLWs storage as calcined powder
Apart from storing as liquid, P2 O5 -HLWs are also stored as calcined powder. Reprocessing of Al/Zircaloy/stainless steel/graphite
cladded spent fuels following PUREX process results in generations of (a) F-rich and (b) Al-rich wastes [47]. To these (i) Aland Ca-nitrates are added for uoride complexations as well as
volatility suppression, and (ii) H3 BO3 is put to prevent insoluble Al2 O3 and -Al2 O3 formation. For volume reduction, P2 O5 -HLWs
are sprayed into hot (400600 C) uidized bed whereupon anions
such as nitrates, carbonates, etc. decompose leading to formation
and growth of multi-oxide calcined particles, which are then piped
pneumatically into underground storage tanks. The nal composition of calcined wastes therefore depends on initial P2 O5 -HLW
compositions and subsequent chemicals added during powder formations. For example, Al-calcines are usually rich in Al2 O3 and
B2 O3 , while Zr-calcines are enriched in CaF2 , ZrO2 , Al2 O3 , CaO
and B2 O3 [48]. Similar calcination route has also being considered for treating NaNO3 rich waste streams (commonly referred as
sodium bearing waste, SBW) which mostly arise from site clean-up
(decontamination and decommission) activities [47]. Compositionally SBW is a HNO3 solution with relatively high concentrations of
NO3 , Na+ , Al3+ , K+ , P2 O5 , and SO4 2 [49].
3. Phosphate in silicate melts
3.1. Lessons learnt from natural melts
As mentioned earlier, borosilicate glasses are generally preferred for HLW immobilization. However, natural analogue studies
21
backed up by experimental observations on equivalent synthetic melts show that P2 O5 even if present in small quantities
(12 wt%) can (i) promote liquid immiscibility (basic and acidic
melts [50,51]), (ii) control trace element partitioning within melts
[52,53], (iii) reduce melt viscosity [54,55], (iv) shift liquidus
boundaries towards silica decient domains within variably polymerized silicate melts [56] and (vi) depress solidus [57]. Raman
investigations in SiO2 P2 O5 system show the presence of isolated non-polymerizedP2 O5 (basic) rich domains connected to
polymerizedSiO2 (acidic) melts through formation of P O Si linkages [58]. In case of aluminosilicate system, the situation changes
as juxtaposition of Al3+ and P5+ promote quartz (SiO2 )berlinite
(AlPO4 ) substitution:
Al3+ + P5+ = 2Si4+
(1)
22
Fig. 6. Phosphate structural units reported from glasses (Qi : i represents number of
bridging oxygen per tetrahedron).
23
Table 3
Compositional dependence of phosphate structure binary in binary xR2 O (or R O)(1 x)P2 O5 (x in mol%) system.
Structure
Ultraphosphate
Mesophosphate
Polyphosphate
Pyrophosphate
Orthophosphate
Compositional
range
Dominating
structural groups
Proportion of
structural groups
x = 0.50
x > 0.50
x = 0.67
x = 0.75
Q2 and Q3
Q2 chains terminated
Q2 form chains
and rings
by Q1 tetrahedra
f(Q1 ) = ((2x 1)/(1 x))
and f(Q2 ) = ((2 3x)/(1 x))
Isolated Q0
3.5
>3.5
>3
Table 4
Compositions (wt%) of some well studied simulated waste loaded phosphate glasses.
Oxide
Na2 O
Al2 O3
P2 O5
B2 O3
BaO
CaO
CeO2
Cr2 O3
CuO
Fe2 O3
K2 O
MnO
PbO
SO3
SiO2
ZrO2
Cl
F
a
SPP22 Pb
SPP23 Pb
IP30LAW
IP30LAW-A
IP30LAW-C
IP40WG
IP40WG-CCIM
21.17
18.39
35.55
4.49
0.01
5.25
0.21
0.04
4.17
.51
0.94
0.43
0.67
1.62
3.79
2.73
0.0
0.0
17.36
21.08
42.34
0.01
5.61
0.20
0.07
4.33
0.52
0.78
0.45
0.53
1.3
52.2
0.0
0.0
0.1
20.0
0.0
0.0
2.9
0.2
0.2
0.5
11.3
52.2
0.0
0.0
0.1
10.0
0.0
0.0
2.9
0.2
0.2
0.5
1.3
52.2
0.0
0.0
3.1
17.0
0.0
0.0
2.9
0.2
0.2
0.5
10.9
51.7
0.1
0.9
0.1
10.3
3.0
0.3
1.4
0.0
0.3
0.3
11.6
50.0
0.0
0.9
10.6
3.2
0.0
1.8
0.0
0.0
4.32
2.35
0.0
0.0
INEEL-SBW [131]
24
Table 5
Some thermal durability parameters for simulated waste loaded Fe phosphate glasses.
Wasteform
Density
(g/cm3 )
Glass transition
( C)
Crystal
formation ( C)
IP30LAW
IP30LAW-A
IP30LAW-C
2.88
2.77
2.871
483
453
487
572
561
605
IP40WG
IP40WG-CCIM
2.76
2.76
430
420
CAB1
CAB2
DR1
DR2
PFeOx
PFeUOx
500
496
497
506
515
535
Liquidus ( C)
Reference
168
165
163
[130]
590
560
740
718
[131]
67.1
78.2
65.3
52.4
90.4
84.7
[119]
25
6. Future challenges
As indicated earlier, restricted solubility of P2 O5 -HLWs (+sulfate) within silicate melts has encouraged wasteform designers
once again to judge the potentiality of P2 O5 based glass systems
as host matrices. A good amount of laboratory based experimental studies on compositionpropertystructure correlations in
various phosphate based glasses and waste glasses have already
been done and the results have identied few formulations within
alumino phosphate and Fe-phosphate systems. Some of these phosphate glasses look very promising as they are chemically durable,
thermally stable and can be processed at moderate temperatures. However, general tendency of phosphate glasses towards
devitrication often considered as a serious shortcoming. Experimental studies dealing with the effect of devitrication on chemical
durability show contrasting results which make it all the more
important to study the dependence of various product durability
parameters (waste loading, density, glass transition temperature,
melting temperature, Youngs modulus, Poisson ratio, Vickerss
hardness, fracture toughness, thermal expansion, thermal conductivity, specic heat, etc.) on crystallization. To reduce the
investigation period substantially it will be a good idea to construct
models capable of predicting crystal nucleation and growth, crystal
compositions and melting behavior for a given formulation, taking
clues from laboratory scale tests. Such models however need to be
calibrated and veried with experimental data obtained from pilot
scale melter trails. While doing this exercise, due considerations
should also be given to the various inuences of radiation damage
processes (with varying doses over different temperature regimes)
on modication of product durability parameters, an aspect so far
neglected in the context of phosphate glass based wasteform.
Another eld where signicant thrust needs to be given is
relevant data acquisition and experience gathering from plant
scale level synthesis of phosphate waste glass matrices. Gaining
such experiences prior to actual plant scale production is necessary so as to avoid severe consequences of faulty manufacturing
operations and/or unsatisfactory wasteform performance. During
laboratory scale experiments with simulated HLWs it is not possible to encounter or anticipate all possible issues that one may
has to face during hot operations. One good example for this is
rapid corrosion and pre-mature failures of furnace components,
especially Alloy 690 components (a variety of NiCrFe superalloy), refractory bricks, etc. during plant scale vitrication of HLWs
over long time scale. Such melt and/or process induced corrosions
26
Acknowledgements
Author gratefully acknowledges Alexander von Humboldt Foundation, Germany. Prof. Andrew J. Daugulis is thanked for carrying
out editorial responsibility very effectively.
References
[1] A. Dahhan, H. Muthanna, Radioisotopes applications in industry: an overview,
Atom Peace 2 (2009) 324337.
[2] Y. Ando, K. Nishihara, H. Takano, Estimation of spent fuel compositions from
light water reactors, J. Nucl. Sci. Technol. 37 (2000) 924933.
[3] V. Grover, P. Sengupta, K. Bhanumurthy, A.K. Tyagi, Electron probe microanalysis (EPMA) investigations in the CeO2 ThO2 ZrO2 system, J. Nucl. Mater. 350
(2006) 169172.
[4] V. Grover, P. Sengupta, A.K. Tyagi, Sub-solidus phase relations in CeO2 YSZ
and ThO2 YSZ systems: XRD, high-temperature XRD and EPMA studies,
Mater. Sci. Eng. B 138 (2007) 246250.
[5] V. Grover, A. Banerji, P. Sengupta, A.K. Tyagi, Raman, XRD and microscopic
investigations on CeO2 Lu2 O3 and CeO2 Sc2 O3 systems: a sub-solidus phase
evolution study, J. Solid State Chem. 181 (2008) 19301935.
[6] T.R.G. Kutty, R.V. Kulkarni, P. Sengupta, K.B. Khan, K. Bhanumurthy, A.K. Sengupta, J.P. Panakkal, A. Kumar, H.S. Kamath, Development of CAP process for
fabrication of ThO2 UO2 fuels. Part II: Characterization and property evaluation, J. Nucl. Mater. 373 (2008) 309318.
[7] T.R.G. Kutty, M.R. Nair, P. Sengupta, U. Basak, A. Kumar, H.S. Kamath, Characterization of (ThU)O2 fuel pellets made by impregnation technique, J. Nucl.
Mater. 374 (2008) 919.
[8] P. Sengupta, P.S. Gawde, K. Bhanumurthy, G.B. Kale, Diffusion reaction
between Zircaloy 2 and Thoria, J. Nucl. Mater. 325 (2004) 180187.
[9] P. Hejzlar, M.J. Driscoll, N.E. Todreas, Impact of fuel choices on spent fuel
characteristics for once through heavy metal cooled reactors, in: Proceedings
of a Committee Meeting (TCM) on Core Physics and Engineering Aspects
of Emerging Nuclear Energy Systems for Energy Generation and Transmutation, Argonne, IL, USA, 28 November 1 December, IAEA-TECDOC-1356,
IAEA, Vienna, 2000, pp. 168185.
[10] E.C. Buck, B.D. Hanson, B.K. McNamara, The geochemical behavior of Tc, Np
and Pu in spent nuclear fuel in an oxidizing environment, in: R. Gier, P. Stille
(Eds.), Energy, Waste, and the Environment: a Geochemical Perspective, vol.
236, The Geological Society of London Special Publication, 2004, pp. 6588.
[11] M. Benedict, T.H. Pigford, H.W. Levi, Nuclear Chemical Engineering, 2nd ed.,
McGraw Hill, New York, 1981, 369 pp.
[12] R. Roy, Ceramic science of nuclear waste xation, Am. Ceram. Soc. Bull. 54
(1975) 459.
[13] N. Das, P. Sengupta, S. Roychowdhury, G. Sharma, P.S. Gawde, A. Arya, V. Kain,
U.D. Kulkarni, J.K. Chakravartty, G.K. Dey, Metallurgical characterizations of
FeCrNiZr base alloys developed for geological disposal of radioactive hulls,
J. Nucl. Mater. 420 (2012) 559574.
[14] P. Sengupta, S. Fanara, S. Chakraborty, Preliminary study on calcium aluminosilicate glass as a potential host matrix for radioactive 90 Sr an approach
based on natural analogue study, J. Hazard. Mater. 190 (2011) 229239.
[15] Parveena, P. Sengupta, R.K. Mishra, C.P. Kaushik, S. Sai, G.K. Dey, Feasibility
study on immobilization of nuclear power plant waste in borosilicate glass
matrix doped with calcium aluminosilicate and titania, J. Nucl. Mater. (2012)
(under revision).
[16] A.E. Ringwood, S.E. Kesson, N.G. Ware, W. Hibberson, A. Major, Immobilization of high level nuclear reactor wastes in SYNROC, Nature 278 (1979) 219
223.
[17] I.W. Donald, B.L. Metcalfe, R.N.J. Taylor, Review: the immobilization of high
level radioactive wastes using ceramics and glasses, J. Mater. Sci. 32 (1997)
58515887.
[18] R.C. Ewing, Radioactivity and the 20th century, in: P.C. Burns, R.J. Finch (Eds.),
Mineralogical Society of America, Reviews in Mineralogy, vol. 38, 1999, pp.
122.
[19] R.C. Ewing, Natural glasses: analogues for radioactive waste forms, in: G.J.
McCarthy (Ed.), Scientic Basis for Nuclear Waste Management, vol. 1, Plenum
Press, New York, NY, 1979, pp. 5768.
[20] R.C. Ewing, L.M. Wang, Phosphates as nuclear wasteforms, Rev. Miner.
Geochem. 48 (2002) 673699.
[21] L.L. Hench, D.E. Clark, J. Campbell, High level waste immobilization forms,
Nucl. Chem. Waste Manag. 5 (1984) 149173.
[22] W.E. Lee, M.I. Ojovan, M.C. Stennett, Immobilization of radioactive waste in
glasses, glass composite materials and ceramics, Adv. Appl. Ceram. 105 (2006)
312.
[23] M.I. Ojovan, W.E. Lee, An Introduction to Nuclear Waste Immobilization,
Elseiver, 2005, p. 315.
[24] M.I. Ojovan, W.E. Lee, New Developments in Glassy Nuclear Wasteforms, Nova
Science Pub Inc., 2007, p. 131.
[25] International Atomic Energy Agency, Spent Fuel and High Level Waste: Chemical Durability and Performance Under Simulated Repository Conditions,
IAEA-TECDOC-1563, IAEA, Vienna, 2007, 29 pp.
[26] International Atomic Energy Agency, Status and Trends in Spent Fuel Reprocessing, IAEA-TECDOC-1467, IAEA, Vienna, 2005, 101 pp.
[27] P. Sengupta, D. Rogalla, H.W. Becker, G.K. Dey, S. Chakraborty, Development
of graded NiYSZ composite coating on Alloy 690 by pulsed laser deposition
technique to reduce hazardous metallic nuclear waste inventory, J. Hazard.
Mater. 192 (2011) 208221.
[28] P. Sengupta, Interaction study between nuclear waste glass melt and ceramic
melter bellow liner materials, J. Nucl. Mater. 411 (2011) 181184.
[29] International Atomic Energy Agency, Design and Operation of High Level
Waste Vitrication and Storage Facilities, Technical reports series no. 339,
1992.
[30] P. Sengupta, J. Mittra, G.B. Kale, Interaction between borosilicate melt and
Inconel, J. Nucl. Mater. 350 (2006) 6673.
[31] P. Sengupta, C.P. Kaushik, R.K. Mishra, G.B. Kale, Microstructural characterization and role of glassy layer developed on process pot wall during
nuclear high-level waste vitrication process, J. Am. Ceram. Soc. 90 (2007)
30573062.
27
[62] C. Nelson, D.R. Tallant, Raman studies of sodium silicate glasses with low
phosphate contents, Phys. Chem. Glasses 25 (1984) 3139.
[63] R. Dupree, D. Holland, M.G. Mortuza, The role of small amounts of P2 O5 in the
structure of alkali disilicate glasses, Phys. Chem. Glasses 29 (1988) 1821.
[64] R. Dupree, D. Holland, J.A. Mortuza, J.A. Collins, M.W.G. Lockyer, Magic
angle spinning NMR of alkali phosphoralumino-silicate glasses, J. Non-Cryst.
Solids 112 (1989) 111119.
[65] D. London, M.B. Wolf, G.B. Morgan VI, M.G. Garrido, Experimental silicatephosphate equilibria in peraluminous granitic magmas, with a case study of
the Alburquerque batholith at Tres Arroyos, Badajoz, Spain, J. Petrol 40 (1999)
215240.
[66] C.M. Jantzen, Investigation of lead-iron phosphate glass for SRP waste, in: D.E.
Clark, W.B. White, A.J. Machiels (Eds.), Nuclear Waste Management, vol. 20,
Adv. Ceram., 1986, pp. 157165.
[67] R.K. Mishra, P. Sengupta, C.P. Kaushik, A.K. Tyagi, G.B. Kale, K. Raj, Thorium in
barium borosilicate glass, J. Nucl. Mater. 360 (2007) 143150.
[68] S.V. Stefanovsky, F.A. Lifanov, Glasses for immobilization of sulfate containing
radioactive wastes, Radiokhimiya 31 (1989) 129134.
[69] W.K. Kot, H. Gan, I.L. Pegg, Ceram. Trans. 107 (2000) 441449.
[70] C.M. Jantzen, M.E. Smith, D.K. Peeler, Dependency of sulfate solubility on melt
composition and melt polymerization, Ceram. Trans. 168 (2005) 141152.
[71] D. Manara, A. Grandjean, O. Pinet, J.L. Dussossoy, D.R. Neuville, Sulfur behavior
in silicate glasses and melts: implications for sulfate incorporation in nuclear
waste glasses as a function of alkali cation and V2 O5 content, J. Non-Cryst.
Solids 353 (2007) 1223.
[72] R.K. Mishra, V. Sudarsan, P. Sengupta, R.K. Vatsa, A.K. Tyagi, C.P. Kaushik,
D. Das, K. Raj, Role of sulphate in structural modications of sodium barium borosilicate glasses developed for nuclear waste immobilization, J. Am.
Ceram. Soc. 91 (2008) 39033907.
[73] V. Kain, P. Sengupta, P.K. De, S. Banerjee, Case reviews on the effect of
microstructure on the corrosion behavior of austenitic alloys for processing and storage of nuclear waste, Metall. Mater. Trans. 36A (2005) 1075
1084.
[74] W.H. Zachariasen, The atomic arrangement in glass, J. Am. Chem. Soc. 54
(1932) 38413851.
[75] J.R. van Wazer, Structure and properties of the condensed phosphates. II. A
theory of the molecular structure of sodium phosphate glasses, J. Am. Chem.
Soc. 72 (1950) 644647.
[76] U. Hoppe, G. Walter, R. Kranold, D. Stachel, Structural specics of phosphate
glasses probed by diffraction methods: a review, J. Non-Cryst. Solids 263 and
264 (2000) 2947.
[77] Y.M. Moustafa, K. El-Egili, Infrared spectra of sodium phosphate glasses, J.
Non-Cryst. Solids 240 (1998) 144153.
[78] R.K. Brow, Review: the structure of simple phosphate glasses, J. Non-Cryst.
Solids 263 and 264 (2000) 128.
[79] G. Walter, G. Goerigk, C. Rssel, The structure of phosphate glass evidenced
by small angle X-ray scattering, J. Non-Cryst. Solids 352 (2006) 40514061.
[80] F.F. Sena, J.R. Martinelli, L. Gomes, Synthesis and characterization of niobium
phosphate glasses containing barium and potassium, J. Non-Cryst. Solids 348
(2004) 3037.
[81] B. Tiwari, M. Pandey, V. Sudarsan, S.K. Deb, G.P. Kothiyal, Study of structural modication of sodium aluminophosphate glasses with TiO2 addition
through Raman and NMR spectroscopy, Physica B: Phys.: Condens. Matter
404 (2009) 4751.
[82] A.G. Blasewitz, G.L. Richardson, J.L. McElroy, J.E. Mendel, K.J. Schneider, Management of Radioactive Wastes from Fuel Reprocessing, Organization for
Economic Cooperation and Development, Paris, 1973, pp. 615654.
M. Gotic,
S. Popovic,
Corrosion of stainless steel in contact with a
[83] S. Music,
melt of phosphate glasses, J. Mater. Sci. Lett. 8 (1989) 13891390.
[84] D.E. Day, C.S. Ray, K. Marasinghe, M. Karabulut, X. Fang, An alternative host
matrix based on iron phosphate glasses for the vitrication of specialized
waste forms, Final report for DE-FG07-96ER45618, Project No: 55110; submitted to The Environmental Management Science Program, US-DOE, 2000,
pp. 39.
[85] D. Read, C.T. Williams, Degradation of phosphatic waste forms incorporating
ling-lived radioactive isotopes, Miner. Mag. 65 (2001) 589601.
[86] A.E. Hadrami, M. Mesnaoui, M. Maazaz, J.J. Videau, Kinetic dissolution of phosphate glasses containing toxic heavy metals, J. Non-Cryst. Solids 331 (2003)
228239.
[87] B.C. Bunker, G.W. Arnold, J.A. Wilder, Phosphate glass dissolution in aqueous
solutions, J. Non-Cryst. Solids 64 (1984) 291316.
[88] R.K. Brow, Nature of alumina in phosphate glass: I. Properties of sodium
aluminophosphate glass, J. Am. Ceram. Soc. 76 (1993) 913918.
[89] S.V. Stefanovsky, I.A. Ivanov, A.N. Gulin, in: T. Murakami, R.C. Ewing (Eds.),
Scientic Basis for Nuclear Waste Management, vol. XVIII, Materials Research
Society, Pittsburgh, PA, 1995, pp. 101106.
[90] S. Wegner, L. van Wllen, G. Tricott, The structure of aluminophosphate
glasses revisited: application of modern solid state NMR strategies to determine structural motifs on intermediate length scales, J. Non-Cryst. Solids 354
(2008) 17031714.
[91] R.A. Merrill, K.F. Whittington, R.D. Peters, Vitrication of High Sulfate Wastes,
Report no. PNL-SA-24672, Pacic Northwest Laboratory, Richland, Washington, 1994, pp. 16.
[92] V.V. Kushinikov, Y.I. Mayunin, N.V. Krylova, The behavior of alpha-emitting
radionuclides in the solidication of high activity waste, Atom. Energy 70
(1991) 239243.
28
A. Santi
S.T. Reis, K. Furic,
D.E. Day, Studies of leadiron
[101] A.M. Milankovic,
c,
phosphate glasses by Raman, Mssbauer and impedance spectroscopy, J. NonCryst. Solids 351 (2005) 32463258.
[102] B.C. Sales, L.A. Boatner, Lead phosphate glass as a stable medium for the
immobilization and disposal of high-level nuclear waste, Mater. Lett. 2 (1984)
301304.
[103] S.T. Reis, D.L.A. Faria, J.R. Martinelli, W.M. Pontuschka, D.E. Day, C.S.M. Partiti,
Structural features of lead iron phosphate glasses, J. Non-Cryst. Solids 304
(2002) 188194.
[104] S.T. Reis, M. Karabulut, D.E. Day, Structural features and properties of
leadironphosphate nuclear wasteforms, J. Nucl. Mater. 304 (2002) 8795.
[105] J. Kliava, R. Berger, J. Trokss, Electron paramagnetic resonance and Mssbauer
effect studies in iron-doped 57 Fe isotope enriched phosphate glasses, J. NonCryst. Solids 202 (1996) 205214.
[106] R. Berger, J. Kliava, E.M. Yahiaoui, J.C. Bissey, P.K. Zinsou, P. Beziade, Diluted
and non-diluted ferric ions in borate glasses studied by electron paramagnetic
resonance, J. Non-Cryst. Solids 180 (1995) 151163.
[107] G.K. Marasinghe, M. Karabulut, C.S. Ray, D.E. Day, D.K. Shuh, P.G. Allen, M.L.
Saboungi, M. Grimsditch, D. Haeffner, Properties and structure of vitried
iron phosphate nuclear wasteforms, J. Non-Cryst. Solids 263264 (2000) 146
154.
[108] D.E. Day, Z. Wu, C.S. Ray, P. Hrma, Chemically durable iron phosphate glass
waste forms, J. Non-Cryst. Solids 241 (1998) 112.
M. Rajic,
A. Drasner, R. Trojko, D.E. Day, Crystallization of
[109] A.M. Milankovic,
iron phosphate glasses, Phys. Chem. Glasses 39 (1998) 7075.
[110] D.E. Day, C.S. Ray, C.W. Kim, Iron phosphate glasses: an alternative for vitrifying certain nuclear wastes, Final report for DE-FG07-96ER45618, Project
No. 73976, submitted to The Environmental Management Science Program,
US-DOE, 2004, p. 20.
[111] M.G. Mesko, D.E. Day, Immobilization of spent nuclear fuel in iron phosphate
glass, J. Nucl. Mater. 273 (1999) 2736.
[112] M. Karabulut, G.K. Marasinghe, C.S. Ray, D.E. Day, O. Ozturk, G.D. Waddill,
X-ray photoelectron and Mssbauer spectroscopic studies of iron phosphate glasses containing U, Cs and Bi, J. Non-Cryst. Solids 249 (1999) 106
116.
[113] M. Karabulut, G.K. Marasinghe, C.S. Ray, G.D. Waddill, D.E. Day, Y. Badyal, M.L.
Saboungi, D. Haeffner, S. Shastri, A high energy X-ray and neutron scattering
study of Iron phosphate glasses containing uranium, J. Appl. Phys. 87 (2000)
21852193.
[114] P.A. Bingham, R.J. Hand, Sulphate incorporation and glass formation in phosphate systems for nuclear and toxic waste immobilization, Mater. Res. Bull.
43 (2008) 16791693.
[115] G.K. Marasinghe, M. Karabulut, C.S. Ray, D.E. Day, M.G. Shumsky, W.B. Yelon,
C.H. Booth, P.G. Allen, D.K. Shuh, Structural features of iron phosphate glasses,
J. Non-Cryst. Solids 222 (1997) 144152.
[116] C.S. Ray, X. Fang, M. Karabulut, G.K. Marasinghe, D.E. Day, Effect of melting
temperature and time on iron valence and crystallization of iron phosphate
glasses, J. Non-Cryst. Solids 249 (1999) 116.
[117] F.J.M. Almeida, J.R. Martinelli, C.S.M. Partiti, Characterization of iron phosphate glasses prepared by microwave heating, J. Non-Cryst. Solids 353 (2007)
47834791.
D.E. Day, Iron redox equilibrium, struc[118] X. Fang, C.S. Ray, A.M. Milankovic,
ture and properties of iron phosphate glasses, J. Non-Cryst. Solids 283 (2001)
162172.
[119] D.O. Russo, D.S. Rodrguez, J.M. Rincn, M. Romero, C.J.R.G. Oliver, Thermal properties and crystallization of iron phosphate glasses containing unto
25 wt% additions of Si-, Al-, Na- and U-oxides, J. Non-Cryst. Solids 354 (2008)
15411548.
[120] T. Murata, M. Torisaka, H. Takebe, K. Morinaga, Compositional dependence of
the valency state of Cr ions in oxide glasses, J. Non-Cryst. Solids 220 (1997)
139146.
A.M. Milankovic,
K. Furic,
V. Bermanec, C.W. Kim, D.E. Day, Structural
[121] A. Santi
c,
properties of Cr2 O3 Fe2 O3 P2 O5 glasses. Part I, J. Non-Cryst. Solids 353 (2007)
10701077.
[122] Y. Zhang, A. Navrotsky, H. Li, L. Li, L.L. Davis, D.S. Strachan, Energetics of dissolution of Gd2 O3 and HfO2 in sodium alumino-borosilicate glasses, J. Non-Cryst.
Solids 296 (2001) 93101.
[123] C. Lopez, X. Deschanels, J.M. Bart, J.M. Boubals, C.D. Auwer, E. Simoni, Solubility of actinide surrogates in nuclear glasses, J. Nucl. Mater. 312 (2003)
7680.
[124] M.G. Mesko, D.E. Day, B.C. Bunker, Immobilization of CsCl and SrF2 in iron
phosphate glass, Waste Manage. 20 (2000) 271278.
[125] X. Fang, C.S. Ray, D.E. Day, Glass transition and fragility of iron phosphate
glasses. II. Effect of mixed alkali, J. Non-Cryst. Solids 319 (2003) 314321.
[126] C.A. Click, R.K. Brow, T.M. Alam, Properties and structure of cesium phosphate
glasses, J. Non-Cryst. Solids 311 (2002) 294303.
[127] K. Joseph, R. Venkata Krishnan, K.V. Govindan Kutty, P.R. Vasudeva Rao, Crystallization kinetic of a cesium iron phosphate glass, Thermochim. Acta 494
(2009) 110114.
[128] K. Ghosh, G.K. DasMohapatra, N. Soodbiswas, Glass formation in
K2 SO4 CaOP2 O5 system, Phys. Chem. Glasses 44 (2003) 313318.
[129] I.A. Ivanov, Diffusion of sodium cations and water resistance of glasses for
immobilizing medium level wastes, Radiokhi 33 (5) (1991) 122127.
[130] C.W. Kim, D.E. Day, Immobilization of Hanford LAW in iron phosphate glasses,
J. Non-Cryst. Solids 331 (2003) 2031.
M.
[131] C.W. Kim, C.S. Ray, D. Zhu, D.E. Day, D. Gombert, A. Aloy, A.M. Milanokovic,
Karabulut, Chemically durable iron phosphate glasses for vitrifying sodium
bearing waste (SBW) using conventional and cold crucible induction melting
(CCIM) techniques, J. Nucl. Mater. 322 (2003) 152164.
[132] C.M. Jantzen, N.E. Bibler, D.C. Beam, C.L. Crawford, M.A. Pickett, Westinghouse
Savannah River Company Report, WSRC-TR-92-346, Rev. 1, 1993.
[133] U.S. DOE, Design, Construction, Commissioning of the Hanford Tank Waste
Treatment and Immobilization Plant, DOE Ofce of River Protection, Richland,
WA, Bechtel National, Inc., San Francisco, CA, 2001, Contract No.: DE-AC2701RV14136.
[134] E. Schiewer, W. Lutze, L.A. Boatner, B.C. Sales, Characterization of leadiron
phosphate nuclear waste glasses, in: L.O. Werme (Ed.), Scientic Basis for
Nuclear Waste Management IX, vol. 50, Mater. Res. Soc. Proc., 1986, pp.
231238.
[135] K. Sun, L.M. Wang, R.C. Ewing, W.J. Weber, Effects of electron irradiation in
nuclear waste glasses, Philos. Mag. 85 (4) (2005) 597608.
[136] R.M. Ezz-Eldin, Radiation effects on some physical and thermal properties of
V2 O5 P2 O5 glasses, Nucl. Instrum. Meth. Phys. Res. Sec. B159 (1999) 166175.
[137] M.I. Ojovan, K.P. Travis, R.J. Hand, Thermodynamic parameters of bonds in
glassy materials from viscositytemperature relationships, J. Phys.: Condens.
Matter 19 (2007) 112.
[138] P.A. Bingham, R.J. Hand, S.D. Forder, A. Lavaysierre, F. Deloffre, S. Kilcoyne, I.
Yasin, Structure and properties of iron borophosphate glasses, Phys. Chem.
Glass. B 47 (2006) 313317.
[139] P.A. Bingham, R.J. Hand, S.D. Forder, Doping of iron phosphate glasses with
Al2 O3 , SiO2 or B2 O3 for improved thermal stability, Mater. Res. Bull. 41 (2006)
16221630.
[140] S. Majumdar, P. Sengupta, G.B. Kale, I.G. Sharma, Development of multilayer
oxidation resistance coating on Nb and Ta, Surf. Coat. Technol. 200 (2006)
37133718.
[141] P. Mishra, P. Sengupta, S.N. Athavale, A.L. Pappachan, A.K. Grover, A.K. Suri,
G.B. Kale, P.K. De, K. Bhanumurthy, Brazing of hot isostatically pressed-Al2 O3
to stainless steel (AISI 304L) by MoMn route using 72Ag28Cu braze, Metall.
Mater. Trans. 36A (2005) 14871494.
[142] T. Okura, T. Miyachi, H. Monma, Properties and vibrational spectra of magnesium phosphate glasses for nuclear waste immobilization, J. Eur. Ceram. Soc.
26 (2005) 831836.
[143] L. Ghussn, M.O. Prado, D.O. Russo, J.R. Martinelli, Crystallization of a niobium
phosphate glass, J. Non-Cryst. Solids 352 (2006) 33913397.
[144] M.I. Ojovan, J.M. Juoi, A.R. Boccaccini, W.E. Lee, Glass composite materials for
nuclear and hazardous waste immobilization, Mater. Res. Soc. Symp. Proc.
1107 (2008) 245252.
[145] M.I. Ojovan, W.E. Lee, Glassy wasteforms for nuclear waste immobilization,
Metall. Mater. Trans. A 42 (2011) 837851.