Study the effect of process parameters in

Uranyl Nitrate Raffinate (UNR) treatment

for improving the filterability of slurry and
reduce generation of active waste
Interim project report submitted to the
Board of studies in Engineering Sciences
For the evaluation of
MID TERM PROGRESS OF M-TECH PROJECT
By
SHRUTI JAIN
ENGG1A202101014
NFC,HYDERABAD

JUNE 2022

1 | Page
 ACKNOWLEDGEMENTS

I express thanks to the following individuals who contributed in various ways for the
completion of my project. I am grateful to my venerated guide Dr. Subhankar Manna for
his continuous support for the project, from initial advice, contacts in the early stages of
conceptual inception & through ongoing advice, encouragement to this day.

I am deeply indebted to my Technology Adviser Shri P. V. S. N. Prudhvi Raju for

providing all kind of support and motivation that has come up with this project.

My deep sense of gratitude to control laboratory personnel, HPU lab personnel for their
analysis for number of samples sent during this period of time.

Special thanks to Shri M. R. Reddy & his team, K.Somaiah, I Pavan Kumar & their
team for timely preparation of experimental set up.

I hereby place on record my heartfelt gratitude to Shri T. K. Sinha, Shri K. Bhomanna,

Shri M. Misra, Smt. Swati Mohan, Shri M. Shiva Kumar for their guidance during the
proposal of the project.

I am very thankful to Shri D. Pramanik (GM,FUELS), Dr. Dinesh Srivastava(CE,NFC)

for their valuable advice in the hour of need, providing the requisite facilities for the project
work.

Finally, my special thanks go to my parents, family members and near and dear, without them
I am nothing.

Date: SHRUTI JAIN

2 | Page
Table of Contents
INTRODUCTION................................................................................................................................ 5
1.1 UO2 PRODUCTION PROCESS IN NUOFP(O),NFC.................................................................5
1.2. MOTIVATION FOR THE RESEARCH WORK........................................................................7
1.3. SCOPE....................................................................................................................................... 9
Chapter 2................................................................................................................................................ 9
LITERATURE SURVEY..................................................................................................................... 9
2.1 TREATMENT OF THE UNR SOLUTION.................................................................................9
2.2 SELECTION OF PROCESS FOR UNR TREATMENT.............................................................15
2.3 PRECIPITATION KINETICS..................................................................................................16
2.4 STUDY OF URANYL NITRATE PRECIPITATION.................................................................19
2.5 LACUNAE BETWEEN PRESENT SCENARIO AND PRESENT NEED..................................26
Chapter 3.............................................................................................................................................. 27
EXPERIMENTS................................................................................................................................ 27
3.2 METHODOLOGY OF EXPERIMENTS...................................................................................28
Chapter 4.............................................................................................................................................. 29
RESULTS AND DISCUSSION........................................................................................................... 29
Chapter 5.............................................................................................................................................. 30
BIBLIOGRAPHY.............................................................................................................................. 30

3 | Page
TABLE OF FIGURES

Figure 1: Variation of pH during precipitation-Flow rate of addition of ammonia is 87 ml/h...22

Figure 2: Variation of pH during precipitation when flow rate of addition of ammonia is 26
ml/h...................................................................................................................................... 22
Figure 3: SEM images of final ADU at different magnification a) 500X b) 5000X c) 50000X 26
Figure 4: Change of pH and uranium concentration in filtrate with time................................27
Figure 5: Schematic diagram of experimental setup.............................................................29
Figure 6: Experimental setup photograph.............................................................................29

4 | Page
1. INTRODUCTION

Nuclear energy is the only large-scale, carbon-free electricity source that a country can
widely expand to produce large amounts of electricity. Indian nuclear power reactors are
fuelled by uranium oxide base fuels. Nuclear Fuel Complex manufactures and supplies fuel
assemblies, core structural components and sub assemblies for nuclear power reactors. The
present flow sheet for the production of Uranium di-Oxide (UO 2) is based on the precipitation
of ammonium di-uranate (ADU).

1.1 UO2 PRODUCTION PROCESS IN NUOFP(O),NFC

The process steps followed in uranium oxide powder production are briefed below:

1.1.1 Dissolution

In this step, SDU/HTUP is dissolved in commercial Nitric acid (12N) under steam heating
and agitation at a temperature of 80-85°C, to yield Crude Uranyl Nitrate Slurry (CUNS) as
per the following reaction:
Na2U2O7 + 6 HNO3→2 UO2 (NO3)2 + 2Na (NO3)+3 H2O
UO3 + 2HNO3 → UO2(NO3)2 + H2O

The dissolver tank is maintained at a negative pressure of 5 to 10 mm WC to prevent

leakages of fine dust and nitric acid fumes. The off gases containing nitric acid vapor and ‘U’
dust are scrubbed in packed columns by contacting with water.
Rejected materials (scrap) like UO2 pellets and UO2 powder and sludge as obtained from the
palletizing plants are also dissolved in commercial Nitric acid to yield Uranyl Nitrate
solution, as per the following reactions:
UO2 + 4HNO3 ® UO2 (NO3)2 + 2NO2 +2H2O
3UO2 + 8 HNO3 ® 3 UO2 (NO3)2 + 2NO + 4H2O

5 | Page
The dissolution of scrap material is highly exothermic and hence does not require external
heating. To control the rate of generation of NOx fumes are scrubbed in by passing through
packed type scrubber.

1.1.2 Solvent Extraction

The crude Uranyl Nitrate Solution (CUNS) is adjusted for Uranium concentration and free
acidity before transferring to the solvent Extraction section. The solvent extraction consists of
two major operations namely Extraction and stripping. Tri –Butyl Phosphate diluted in
kerosene (33%TBP, 67% kerosene) is used as solvent.
In the extraction operation, the organic is admitted counter currently to the aqueous feed, in a
ratio of 2:1. Solvent loading to the extent of 85% with uranium is maintained to achieve
nuclear grade extract and keeping uranium losses in the raffinate to a minimum Nuclear grade
Uranyl Nitrate Pure Solution (UNPS) is taken out from the unit at one end and the lean
solvent, taken out from the other end, is recycled back to Extraction process. The Uranyl
Nitrate Raffinate (UNR) generated in the process, containing all the undissolved solids, is
neutralized with ammonia vapor up to 8 pH. The resultant slurry is filtered and the cake
(Uranyl Nitrate Raffinate Cake) is calcined is Processed Uranium Cake Furnace and
dispatched to IREL for Uranium recovery. The Ammonium Nitrate Filtrate is sold to private
parties.

1.1.3 Stripping

In the stripping operation the nuclear grade pure extract is counter currently treated with
demineralised water in box type mixer settler unit where Uranium is transferred back to the
aqueous phase. In this process, the uranium is stripped back from the organic phase (Extract)
to the aqueous phase by using de-mineralized water, in air lift mixer settler type of contactor,
with 10 stages and O/A ratio of 1 is maintained. The solution thus obtained is called Uranyl
Nitrate Pure Solution (UNPS).

1.1.4 Precipitation

6 | Page
The UNPS is precipitated with vapour ammonia in batch mode, wherein required quantity of
UNPS is heated to 60°C, by steam in coil heating. Ammonia is added slowly under gentle
agitation ensuring uniform distribution and the reaction is allowed to proceed till a pH of 8.3
is achieved. Sedimentation or settling tests of the ADU slurry is carried out and 500 ml of the
slurry should settle to 75 ml in 5 minutes.

1.1.5 Filtration

The ADU slurry is filtered in a horizontal pan filter under a vacuum of about 450 mmHg. The
Ammonium Nitrate filtrate obtained is coagulated with ferric chloride and allowed for
settling. The supernatant ammonium nitrate is sold to private parties.

1.1.6 Drying

The ADU cake, from the filter unit is dried in spray drier. The hot off gases, containing
Uranium bearing dust are passed through bag filter, pre-filter and HEPA filter before being
let out through high-rise stack.

1.1.7 Reduction
In this step, ADU powder is reduced to UO2 at about 575°C in a rotary furnace using cracked
ammonia as reducing agent. The furnace is maintained at positive pressure of about 100 mm
WC to prevent ingress of air into the furnace to avoid explosion condition. N2 sealing is used
to avoid leakages.

1.2.9 Stabilization

UO2 is pyrophoric in nature. Therefore, a controlled surface oxidation step is carried out
using air (air and N2 mixture) in a stabilization furnace to prevent bulk oxidation of UO 2
powder. This is carried out at room temperature in a rotary kiln by adopting counter current
between air and UO2 powder. Powder is characterized for morphology, phase homogeneity,
purity, particle size distribution, and specified surface area. The exit gases passed through a
dry scrubber and wet scrubber to restrict uranium bearing dust to go in to atmosphere.

7 | Page
1.2. MOTIVATION FOR THE RESEARCH WORK

Nuclear grade UO2 powder being produced at NFC must satisfy stringent requirements of
Uranium purity. Uranium is purified by solvent extraction (SES) followed by a stripping
process. Nuclear pure uranium solution obtained from stripping is called Uranyl Nitrate Pure
Solution (UNPS). UNPS is further processed to produce UO 2 powder through different hydro
and pyro metallurgical processes. Uranium lean aqueous solution (U <2 gpl) containing most
of the impurities coming out from the extraction unit is called Uranyl Nitrate Raffinate
(UNR).
Treatment of the UNR solution is one of the challenging tasks being faced by nuclear
industries. It is always desirable to recover all the uranium from such dilute solutions not only
for its strategic value as fuel for nuclear reactors but also to meet the stringent disposal
standards.
UNR generated from the solvent extraction section is currently precipitated in a 7.5m3 batch
reactor with vapour ammonia at NUOFP (O), NFC. End pH of 8.0 is ensured for maximum
‘U’ precipitation. The slurry is then filtered using filter aid in Rotary Vacuum Drum Filter
(RVDF). The precoat needs to be applied over the RVDF for better filtration rate. But fine
particles of the precipitated slurry are choking the precoat. It leads to high precoat
consumption, thus increasing the volume of active waste (UNRC). About 650 kg of UNRC
per ton of UO2 powder is being generated, which is very high. It leads to accumulation of
huge quantities of UNRC drums. This is the burning issue not only in NFC but also in other
DAE organizations. Therefore, it is deemed desirable to study the effect of process
parameters in Uranyl Nitrate Raffinate (UNR) treatment to improve the filterability of slurry
and reduce the generation of active waste.

8 | Page
HTUP/SDU/UOC DISSOLUTION
+ HNO3
CUNS

DM Water FEED PREPARATION

UNF
Raffinate Area of
SOLVENT EXTRACTION
TBP+Kerosene (Impurities)
Study
Extract

DM Water STRIPPING
UNPS

Vapor NH3 PRECIPITATION

ADU Slurry

DRYING

ADU
Powder

Cracked NH3 DIRECT REDUCTION

UO2 Powder

STABILISATION

STABILIZED UO2

1.3. SCOPE

9 | Page
The scope of this project is divided into the following specific areas of study:
a) Conduct experiments to study the effect of different process parameters (temperature and
flow rate of vapor ammonia), the effect of multiple precipitation, the effect of coagulants,
and the use of different alkalis (like CaO& MgO) to reduce the generation of active waste.
b) Optimization of process parameters for improved filterability of slurry at plant scale.
c) Implementation of the study in regular plant operation.

10 | Page
Chapter 2
LITERATURE SURVEY

Nuclear grade UO2 powder being produced at NFC must satisfy stringent requirements of
Uranium purity. Uranium is purified by solvent extraction (SES) followed by a stripping
process. Nuclear pure uranium solution obtained from stripping is called Uranyl Nitrate Pure
Solution (UNPS). UNPS is further processed to produce UO 2 powder through different hydro
and pyro metallurgical processes. Uranium lean aqueous solution (U <2 gpl) containing most
of the impurities coming out from the extraction unit is called Uranyl Nitrate Raffinate
(UNR).

2.1 TREATMENT OF THE UNR SOLUTION

A challenging task for nuclear industries is the treatment of UNR solutions. Not only is it
desirable to recover all the uranium from such dilute solutions for its strategic value as fuel
for nuclear reactors, but it is also necessary to meet the stringent disposal standards.
To accomplish this, the following methods can be used:

2.1.1 Evaporation
Evaporation is the process by which a solution or slurry is concentrated via boiling away the
solvent. It is a unit operation that has wide application in the nuclear industry for reducing
waste volumes and for reducing the amount of radioactive nuclides in liquid effluents.
Evaporation is usually used for radioactive wastes that require the high degree of separation
between volatile and nonvolatile components that it offers or for wastes that are not amenable
to treatment by low-temperature operations such as precipitation, filtration, and ion exchange.
An evaporator consists basically of a device to transfer heat for boiling the solution or slurry
and a device to separate the vapour phase from the liquid phase.

It is a proven method for the treatment of liquid radioactive waste providing both good
decontamination and volume reduction. It is probably the best technique for wastes having
relatively high salt content with a wide heterogeneous chemical composition. [1].This

11 | Page
treatment method leads to decontamination factors in the range 104 – 106. Although it can be
considered a fairly simple operation which has been successfully applied in the conventional
chemical industry for many years, its application in the treatment of radioactive waste can
give rise to some problems such as corrosion, scaling, or foaming. Such problems can be
reduced by appropriate provisions. For example, the pH value can be adjusted to reduce
corrosion; organics can be removed to reduce foaming or anti-foaming agents can be added;
and the evaporator system can be cleaned by nitric acid to eliminate scaling and subsequent
passivation of construction material. Surface-active agents can be used in collecting metal
ions by foam separation. Kim et al. [2] demonstrated that the average recovery of uranium by
this method was around 82%. However, it is difficult to recover the surface-active agents
after use. They recommend flotation made with coagulants such positively charged ferric
hydroxide with an anionic surfactant as, sodium dodecyl sulfate. However, it is difficult to
recover the surface-active agents after use.

2.1.2 Ion Exchange

In Ion Exchange method, the separation of uranium can be carried out with higher yields by
the ion exchange resins. The use of ion exchange for radioactive clean-up is recommended
for aqueous solutions with low TDS (Total Dissolved Salts) and particulates and colloids
free. [3]

Liquid radioactive wastes usually have to satisfy the following criteria to be suitable for ion-
exchange treatment: the concentration of suspended solids in the waste should be low; the
waste should have low (usually less than 1 gram per litre) total salt content; and the
radionuclides should be present in suitable ionic form. (Filters pre-coated with powdered
resin can be used to remove colloids).

Emefrenkov[1] found that in most technical systems, ion-exchange processes are applied
using a fixed bed of ion-exchange material filled in a column, which is passed through by the
contaminated effluent either from top to bottom or vice versa. The ion-exchange material
may be regenerated after having reached saturation of the active groups (breakthrough
capacity). Some types of ion exchangers are also removed as waste concentrate to be
solidified. Therefore the ion-exchange process represents a semi continuous process and

12 | Page
requires major efforts in maintenance like flushing, regeneration, rinsing, and refilling
operations.
Bunus, 1976 [4] show that Amberlite IRA 400 has an exchange capacity of approx. 300 g/l,
and that the environmental acidity reduces the capacity to 50 g/l. In the case of alkaline
attack, uranyl ion is in the anionic form of [UO 2(CO3)3]4- at low concentrations, when it will
use anionic resin, too. The use of cationic resin is possible in acidic medium, at low acidity,
pH 2.5-3, when prevail UO22 +.
Sodaye et al.,2009 [5] reported that resins having complexing reagents, such as 8-
hydroxyquinoline or resorcinol arsenic acid formaldehyde, show a very good uptake of
uranium.

2.1.3 Sorption

Uranium can be extracted using a variety of adsorbents.

TiO2
Titanium oxide (TiO2) is one of the earliest adsorbents explored for uranium extraction. For
the elution of the adsorbed uranium, acids such as hydrochloric acid and sulfuric acid and
solutions of carbonates as ammonium carbonate, sodium carbonate and sodium bicarbonate
can be used. The rate of elution by acid (e.g., 0.2 N HCl) is slower than that by using
carbonate. With 1 N ammonium carbonate it needs 48 h for eluting more than 90% of the
adsorbed uranium at room temperature. The crystalline microporous titanosilicates have a
high potential for these decontaminations.

Activated carbon
Adsorption of uranium from water has been proven to be very effective with activated
carbon. However, the adsorption rate of a particular activated carbon can vary dramatically,
depending upon the original carbon source material used: the pyrolysis method and the
activation method . The advantage of activated carbon is in the elution process, where carbon
will not dissolve in the more concentrated eluents. The second method of recovery would be
to burn the carbon in a conventional coal fired turbine or gasify, leaving an ash which is
highly concentrated uranium ore. In 2012, Foo et al. [6] showed that the feasibility of
activated carbon adsorption processes for the remediation of uranium contaminated water has

13 | Page
been well proven by a number of laboratory and pilot scale studies, but great progress in this
area can be expected in the future.

Galena (PbS)
C.-K. Yun, 1982 [7] reported that galena is a better adsorbent than hydrous titanium oxide.
The adsorption capacity of reagent grade galena is around 1100 g/g PbS as compared to
adsorption capacity of hydrated titanium oxide of 600 g/g of TiO 2 . The adsorption
performance of the galena is not affected by repeated use as it is regenerated by use of dilute
hydrochloric acid [8].

2.1.4 Membrane Separation

Membrane processes, particularly reverse osmosis (RO) and ultrafiltration (UF), have been
found to be very useful in recent years in the treatment of aqueous effluents (I) in addition to
their predominant role in desalination (2) and the food processing industries (3). Reverse
osmosis, an inherently simple operation with built-in flexibility for adopting a combination of
membranes and module configurations, has good potential for various separation applications
in the process industry. Because it is an ambient temperature rate-governed process, it is
ideally suited for adoption in the nuclear industry, particularly for effluent treatment. The
membrane processes are particularly attractive because they can divide the initial effluent into
two streams: the permeate stream with low concentrations of uranium, suitable for discharge,
and the concentrated stream containing sufficiently higher concentrations of uranium,
permitting economic recovery.In addition, the reverse osmosis process can bring down the
concentration of nitrates, unlike the lime treatment process where only the uranyl species is
adsorbed to the permissible level of discharge and a denitrification step may have to be
adopted.
Prabhakar et. al [10] found that membrane processes, particularly reverse osmosis, have a
potential for the concentration/decontamination of uranyl solutions. He also suggested in
order to reduce the permeate concentrations to less than 1 mg/L, a two-stage reverse osmosis
would be better, with the second stage operating with additives, preferably EDTA. It was
well established that additives improve membrane performance. The performance of
cellulose acetate membranes had been found to be on par with commercially available
polyamide membranes when additives were used.

14 | Page
Hsiue et al., 1989 [11]reported on the use of RO membranes to treat uranium conversion
process effluent containing toxic, corrosive, and radioactive compounds. The FT30 (Filmtec )
membranes studied had rejections of uranium ≥99.5% for water recoveries up to 70%, and
the results indicated that the treated effluent would meet regulatory discharge standards.
Chu et al., 1990 [12] used a three stage process consisting of nanofiltration, reverse osmosis,
and precipitation to treat uranium effluents. The process removed both soluble and suspended
uranium species; it was found that 95% uranium recovery was possible, and the treated
effluent met environmental standards. Since even the molecular weight of the uranyl cation,
which is the lightest uranium compound in water, is above the typical molecular weight cut-
off of NF membranes, it can be expected that the rejection of other uranium compounds, not
investigated, would also be above 90 or 95%.
Raff et Wilken, 1999 [13] was determined the rejection of the most important uranium
species for the mobilization of uranium generated in different model waters, using a broad
spectrum of commercially available NF membranes. They showed that the most important
uranium species in natural water can be removed to about 95% over a wide range of pH and
hydrochemical setting. Since even the molecular weight of the uranyl cation, which is the
lightest uranium compound in water is above the typical molecular weight cut-off of NF
membranes, it can be expected, that the rejection of other uranium compounds, not
investigated, would also be above 90 or 95%.

2.1.5 Biological Separation

Radioisotopes recovery from wastewater by microorganisms is performed by adsorption on
the surface and intracellular accumulation. The accumulation ability depends on many
physicochemical and biological factors. The uranium recovery methods by biological
separation, tested at pilot scale, use microorganisms like Leptospirillum thiooxidans,
Thiobacillus ferooxidans, Thiobacillus thiooxidans, separate or admixture, and Thermophile
or Heterotrophic bacteria [14, 15]. The maximum loading obtained in the case of
Pseudomonas sp. is 24.5% g (245 mg-U/g dry biomass) dry wt of the biomass at pH 3.5 and
for Talaromyces mersonii CBS 814.70 it is 323 mg-U/g dry biomass.The adsorption process
follows Langmuir adsorption and the equilibrium reaches in 2 min [16].

2.1.6 Solvent Extraction

15 | Page
The solvent extraction is not novel in Uranium processing, it has been used in the purification
process and as a processing method of spent nuclear fuel. Extraction processes originate in
the discovery of the property of uranium nitrate to be readily soluble in diethyl ether and
extraction of uranium with ether was used as a method for the purification of uranium nitrate
samples.[9]
In a typical aqueous-based reprocessing of used nuclear fuel, the aqueous phase containing
dissolved fuel is contacted with an organic phase containing tri-n-butyl phosphate (TBP).
The generally accepted overall mass action mechanism involved in the extraction process is
summarized as the following:
(UO2 2+)aq + 2(NO3)aq + 2(TBP)org —> (UO2(NO3)2.2TBP)org (1)
In (1), UO22+ and NO3 are present in the aqueous phase, TBP is supplied by the organic phase,
and the product, UO2(NO3)2.2TBP, accumulates in the bulk organic phase.

Tachi Sato[17] investigated the effects of nitric acid concentration, uranyl nitrate
concentration, and temperature in order to determine the optimum conditions for the
extraction of uranyl nitrate from nitric acid solutions by TBP. It was apparent from the results
that greater than 97 percent extraction was obtained when uranyl nitrate solution of less than
10 g/1 concentration and containing 6 M HNO3 is extracted with 19 per cent TBP in kerosene
at a temperature of less than 20°C. It was observed that the extraction of uranyl salt into TBP
is increased by the presence of the common nitrate ion and when the extraction temperature is
low the partition coefficient is large, and that it decreases with increasing temperature. Above
20°C the percentage extraction falls below 97 per cent. It is desirable therefore that the
extraction of uranyl nitrate be carried out at less than 20°C.

2.1.7 Precipitation

Chemical precipitation methods based on the coagulation-flocculation separation principle

are mostly used in nuclear power plants for the treatment of liquid effluents with low activity
and high salt and mud contents. Their effectiveness depends largely on the chemical and
radiochemical composition of the liquid waste. Most radionuclides can be precipitated, co-
precipitated, and adsorbed by insoluble compounds, e.g. hydroxides, carbonates, phosphates,
and ferrocyanides, and so be removed from the solution. The precipitates also carry down

16 | Page
suspended particles from the solution by physical entrainment. However, the separation is
never complete for several reasons, and the decontamination factors achieved can be
relatively low. For this reason, chemical treatment is usually used in combination with other
methods.[1]

The precipitation treatment requires the solubility product to be achieved and the
radionuclides to be removed as insoluble compounds. Acid solutions can be precipitated with
alkali metal hydroxides, ammonia, reduction to U (IV) followed by phosphate precipitation,
or by adding hydrogen peroxide and precipitating. In the case of alkaline solution,
precipitation can be achieved by acidification and heat decomposition of the carbonate or by
subsequent addition of alkali hydroxides or ammonia.[9].

2.2 SELECTION OF PROCESS FOR TREATMENT

OF URANYL NITRATE RAFFINATE SLURRY
Different processes like evaporation, ion exchange, sorption, membrane separation ,solvent
extraction may not be feasible or economical to adopt here because of following reasons-
Evaporation-Despite the fact that evaporation is a highly efficient method and also reduces
wastewater volume but it is still an expensive method due to its high energy consumption,
high capital, energy, and maintenance costs, large size of apparatus, high temperatures,
corrosion problems, and scaling or foaming. Moreover, the concentrated slurry if recycled
may choke the pipelines. Therefore, it may not adopted for treatment of UNR Raffinate.
Ion Exchange- The use of ion exchange for radioactive clean-up is recommended for
aqueous solutions with low TDS (Total Dissolved Salts) and particulates and colloids free.
[3] But UNR has high TDS around 60 g/l. Furthermore, the disposal of spent ion exchange
resin is another major issue. Thus, it may not be feasible to adopt for treatment of UNR.
Sorption- The process of sorption can not be employed here for UNR treatment because the
sorbed uranium cannot be easily recovered from the adsorbate. Thus a new waste will be
generated from this process, which is again difficult to process. The process is also costly due
to the huge requirement for chemicals at industrial scale.
Membrane Separation- The technique cannot be used here due to the high membrane waste
generation, which is a major concern for disposal. Furthermore the large particle size of

17 | Page
insolubles may clog membrane pores, thus increasing the pressure drop for filtration and
reducing its efficiency.
Solvent Extraction- In NFC, the UNR generated (U<2gpl) is treated with treated Lean
solvent (U<0.1 gpl) in cross flow to its disposal limit of 4.8 mgpl. This can be directly
disposed of to private companies. But the utilization of SDU Crude Uranyl Nitrate Solution
in plant has resulted in the following UNR treatment issues-
1. Number of extraction stages required for the treatment of UNR has increased from 6 to
12.
2. Increased settling times due to emulsion formations and phase separation issues during
preparation of Treated Lean Solvent (TLS with U < 0.1gpl) from Lean Solvent (LS with
U ~ 14 gpl) with Na2CO3.
3. Recycle of dilute extract and wash solution generated after treatment of lean solvent into
production line has resulted in decreased sintered recovery of UO2 pellets.
The treatment of UNR via solvent extraction has been discontinued.
Precipitation- Having analyzed all the possible methods and their related issues for UNR
treatment, precipitation has been selected as a method for UNR treatment.
UNR treatment at NUOFP(O) is being carried out by precipitating it with vapor ammonia for
U recovery, followed by slurry filtration. Filtrate and the wet cake are called UNR Filtrate
(UNRF) and UNR Cake (UNRC) respectively. The generated UNRC is calcined in Processed
Uranium Cake(PUC) furnace and disposed to IREL for Uranium extraction. UNRF is
disposed through sale to private parties.

2.3 PRECIPITATION KINETICS

Nucleation, growth, agglomeration and breakage are the main kinetics of precipitation. The
primary particle formation process occurring during crystallization and precipitation is firstly
nucleation, which determines the initial formation of crystals, and secondly crystal growth,
which determines their subsequent size. Important secondary processes can also occur.
Particle disruption can occur by which existing particles are broken down into a larger
number of smaller fragments. The latter process is also related to secondary nucleation, an
additional mode of nucleation particularly prevalent in industrial crystallizers. Agglomeration

18 | Page
is a particle size enlargement process by which fine particles, rather than ions or molecules,
are joined in an assembly.

Nucleation-
The formation of a crystal in a homogeneous fluid requires that an energy barrier be scaled.
The total excess free energy between a solute particle and the solute in solution is the sum of
the surface excess free energy and the volume of excess free energy. The excess free energy
tends to be minimised, and this is accomplished through crystal growth or dissolution. The
energy necessary to form a new crystal is called the critical free energy, which is a maximum
on a free energy diagram. If the number of molecules which come together in solution is less
than the number required to reach the critical free energy, then the cluster will redissolve.
This molecular interaction is proportional to the supersaturation, which is the measurable
quantity that gives rise to nucleation and growth of crystals. Crystal formation can result from
homogeneous nucleation, heterogeneous nucleation, secondary nucleation, and attrition.
Homogeneous nucleation is the formation of crystals as a result of only supersaturation.
Heterogeneous nucleation is the formation of new crystals from the presence of
submicroscopic, insoluble, foreign matter, and occurs at lower levels of supersaturation than
is required for homogeneous nucleation. At still lower levels of supersaturation secondary
nucleation takes place, which is the formation of new crystals induced by the interaction of
suspended solute crystals. And finally, attrition is the mechanical degradation of crystals
whose pieces become growing crystals.

Crystal Growth
Crystal growth from solution requires two successive steps, a diffusional transport step to the
crystal surface and a surface reaction step in which the molecule is oriented into the crystal
lattice. The growth rate is said to be diffusion-controlled if the growth rate is limited by the
rate of diffusion through a laminar film as is usually the case in non agitated systems.
However, in some agitated systems the growth rate will reach a maximum as the agitation
increases, which is consistent with the concept of diffusion-controlled growth at low relative
solution velocities and surface reaction controlled growth at high relative velocities.

Agglomeration and Breakage

19 | Page
Generally, particle aggregation, and thus the stability of the system, is determined by the
forces that exist between the solid particles in the dispersion. These forces between particles
can be repulsive or attractive. [19] The attractive forces are of the nature of van der Waals
forces between the atoms in two approaching colloidal particles. The magnitude of this effect
is inversely proportional to the second power of the separation distance between the two
particles. The repulsive forces arise from the electromagnetic interactions of the charged
layer surrounding the particles, the so-called electrical double layer. On the surface of the
particles, a charged layer may be formed due to selective adsorption of ions. This part of the
double layer is immobile and consists of tightly adsorbed ions in direct contact with the
particle surface. In the solution adjacent to the particle, a second layer, in which the ions are
more diffusely distributed, penetrates into the liquid. This part of the double layer is termed
the diffusion layer. The extent of this diffusion layer depends on the electrolyte
concentration: increasing electrolyte concentration causes this diffuse double layer to shrink
closer into the particle, so that the electrostatic potential falls off more quickly with distance.
The process by which the particles are stabilised by the repulsive forces of the electrical
double layers is known as electrostatic stabilisation.

These kinetic parameters (nucleation, growth, agglomeration and breakage) in turn have an
effect on the morphology, size distribution and other properties. The most significant factors
affecting the kinetic parameters are the flow field pattern, mixing, residence time,
temperature, concentration, degree of supersaturation, and suspension density. [20]

UNR Precipitation involves reaction of UNR with vapour ammonia followed by filtration of
slurry using rotary drum vacuum filter. This type of precipitation, which involves chemical
reaction, is called reactive precipitation. In reactive precipitation, a solution of one reactant
often is mixed with a solution of the other, and the product is formed in concentrations
exceeding the solubility. This means supersaturation of product is generated by chemical
reaction. In most practical applications, the properties of the precipitated particles are of key
importance and great attention must be paid to "particle design" or "crystal engineering".
Many crucial properties of precipitates are physical in nature. The crystal size distribution
and crystal habit or morphology can have a major impact on the post-precipitation
processing, such as filtration, drying, etc. In addition to particle design, one needs to ensure
reproducibility of particle properties from batch to batch. This is of particular importance if

20 | Page
the product is subject to statutory or regulatory requirements, as is the case of
pharmaceuticals, nuclear industries etc. In all industrial applications, significant challenges
still exist in scaling up the precipitation processes that involve fast chemical reaction of
concentrated reactants.

2.4 STUDY OF URANYL NITRATE PRECIPITATION

The study on precipitation of Uranyl Nitrate Raffinate(UNR) specifically has not been done
yet to the best of the knowledge. However a literature survey on the precipitation of Uranyl
Nitrate Pure Solution(UNPS) i.e. ADU Precipitation is presented here.

2.4.1 Effect of Free Acidity, temperature and flow rates on characteristics

of ADU

2.4.1.1 Effect of free acidity

Raju et al. [25] studied the effect of free acidity on the quality of ADU powder. Based on the
experiments done, it was derived that as the free acidity in UNPS was increasing, mean of
particle size distribution (of ADU powder) was decreasing i.e. specific surface area of
produced U3O8 powder was increasing.

2.4.1.2 Effect of temperature and flow rates

Murty et al. [26] carried out batch precipitation of ADU at various temperatures and at
different flow rates of ammonia and their effects on the characteristics of ADU such as the
nature of settling, moisture content, ammonia-to-uranium mole ratio and nitrate content were
studied.

21 | Page
 Figure 1: Variation of pH during precipitation-Flow rate of addition of ammonia is 87 ml/h

Figure 2: Variation of pH during precipitation when flow rate of addition of ammonia is 26 ml/h

At low precipitation rates, dispersion of the precipitate particles was favored at low
temperature and agglomeration was favored at high temperatures. Low precipitation rates
were preferred in view of the sinterability requirement of final uranium dioxide powder
derived from ADU. At high precipitation rates, agglomeration was favored at low as well as
high temperatures. Those findings were significant in terms of cost of heating and of the
precipitating agent ammonium hydroxide. The effect of temperature of precipitation on other

22 | Page
important characteristics of ADU was also discussed, bringing out the implications with
respect to energy consumption on a large scale of production. The exponential dependence of
precipitation time on the temperature of ADU precipitation was emphasized.

a) Ammonia required for precipitating “w” g of uranium completely as stoichiometric

ADU was readily calculated from the following equation.

2UO2(NO3)2 + 6NH4OH →(NH4)2U2O7 + 4NH4NO3 +3H2O

and was given by 12.6 w/n where “n” is the normality of ammonia used as precipitant.
For the case, i.e. to precipitate 120 g of uranium using 7.4 N ammonia, the volume required
worked out to be 204 ml. However, at low temperature of precipitation, the consumption of
ammonia for complete precipitation of uranium was only about 80% of this quantity. This
indicated that the actual requirement of ammonia for precipitating uranium completely was
considerably less than that dictated by following equations.. This fact was also revealed by
the experimentally observed low ammonia-to uranium mole ratios for various ADU powders.
Therefore, the following alternative equations were proposed for describing the ADU
precipitation in reality.

3UO2(NO3)2 + 7NH4OH →(UO3)3.(NH3).4H2O+ 6NH4NO3

2UO2(NO3)2 + 5NH4OH →(UO3)2.(NH3).3H2O+ 4NH4NO3

b) Settling Rate- The slurry obtained at a higher temperature of precipitation settled

faster compared to that obtained at a lower temperature. However, the difference in settling
rates was considerable only when the rate of addition of ammonia was slow. At high flow
rates of addition of ammonia, the settling rate of the ADU slurry did not seem to be
dependent on the temperature. The settled volume at a given instant was observed to bear a
linear relation with temperature of precipitation.
c) Moisture Content-The moisture content in the ADU obtained at higher temperature of
precipitation was found to be more compared to that obtained at a low temperature. The
difference in the moisture contents of ADU obtained at two distinct temperatures was quite
high when the flow rate of addition of ammonia was low. The moisture content in the ADUC
at a given temperature of precipitation varied with flow rate of addition of ammonia and it
was observed that the moisture content was more for a higher flow rate.

23 | Page
d) Nitrate Content-The nitrate content in ADU did not seem to vary considerably with
variation in temperature of precipitation when the rate of flow of ammonia was low. At
higher flow rate however, there was a marginal increase with increase in temperature of
precipitation ammonia-to-uranium mole ratio.

Paik et al. [27] investigated the effect of ammonium nitrate on precipitation of ADU from
nitric acid medium via gaseous ammonia route. Studies on the effect of ammonium nitrate on
precipitation time, particle size, shape, surface morphology, flow ability, oxygen/uranium
(O/U) ratio and tap density of calcined ADU were carried out at various ammonium nitrate
concentrations. Their investigation reveals that with increase in ammonium nitrate
concentration in aqueous phase, the precipitation time was increased due to buffer action of
excess ammonium nitrate in alkaline pH range.

2.4.2 Different methods of precipitation

Rajagopal et al.[28] did precipitation by two methods-a) Homogeneous method and b)

Conventional method. In the conventional method of precipitation, 10 ml of 10% NH 4OH
(v/v), was added drop by drop to a 90 ml solution of uranyl nitrate (4 mg/ml uranium and pH
2.0). 1.0 g of ammonium nitrate was added and the solution was digested in a water bath for
an hour, and left overnight. Precipitation was also carried out in 20% and 70% methanol,
ethanol, isopropanol and dioxane. In the homogeneous method of precipitation, instead of
adding NH4OH, ammonia was generated in situ by hydrolysis of urea, by keeping the uranyl
nitrate solution containing urea, in a boiling water bath for two hours. Precipitation was also
done in the presence of organic solvents, as above.
It was seen that particles of ammonium uranate prepared by the homogeneous method were
smaller in size than those prepared by conventional method, which was corroborated by
scanning electron microscopic measurements of the ammonium diuranate precipitated from
aqueous solutions by the conventional and homogeneous methods of precipitation. It
appeared that the precipitates obtained by a conventional method were agglomerated. The
agglomeration further increased on drying at 105°C. When these uranates were ignited at
850°C the oxide obtained had a smaller particle size. In the homogeneous method, the
agglomeration of the uranates was very much less compared to that prepared by the
conventional method. When these uranates were dried or ignited at 850°C there was only
marginal change in particle size. The physical characteristics of the ammonium uranates

24 | Page
prepared from homogeneous solution at lower percentage of solvents, methanol, ethanol, and
isopropanol were found to be better compared to that precipitated from aqueous medium
alone. They were easily filterable, compact and free flowing in nature. The size of the
particles was bigger. The particle size of the U 3O8 obtained from these uranates was greater
than that prepared by the conventional method. It was also observed that the particles were
uniformly distributed and not agglomerated. Thirdly the particle size didn’t alter significantly
on ignition to oxide. Finally it was concluded that the precipitation of ammonium uranates by
the homogeneous method in mixed solvent media methanol, ethanol and isopropanol was
suitable to prepare oxide with better physical characteristics.
Fujino et al. [29] studied a wet precipitate method to form ADU which contains Mg
homogeneously. The method consisted of addition of ammonia water to the solution in which
uranyl nitrate, NH4NO3 and Mg (NO3)2·6H2O are dissolved. In the ADU precipitate taken by
filtration, a small volume of Mg nitrate solution was held. The precipitate was subsequently
dried. The relevant condition was obtained for 10 ml solution of 0.21 M uranyl nitrate in
0.014 M HNO3.
1. The increase of the volume of the uranyl nitrate solution by the addition of NH 4NO3 and
Mg(NO3)2·6H2O was measured. The inequality relations between [Mg2+] sat and [Mg2+] were
calculated.
2. In situ drying of ADU in glass filter in air-bath of 120°C resulted in formation of solids
with much lower Mg concentrations, which is due to melting of Mg(NO 3)2·6H2O at 89°C.
The best result to yield homogeneous fine powder was obtained which comprises drying of
ADU in a rotary-pump vacuum for 24 h at room temperature.
3. The maximum Mg concentration in ADU was obtained at 3±4 ml addition of 25 wt%
ammonia water, which is the least sufficient volume, for 11.8 g NH 4NO3 and 1±3 g
Mg(NO3)2·6H2O. Further addition of ammonia water caused a decrease of Mg concentration
in ADU on account of dilution of Mg concentration in the solution. Precipitation of Mg(OH) 2
did not occur until 40 ml addition of ammonia water.
4. The concentration of Mg in ADU was proportional to the weight of Mg(NO 3)2·6H2O
added for the solution with 2 g NH4NO3 and 5 ml of 25 wt% ammonia water. With 0.5 g
Mg(NO3)2·6H2O, the Mg concentration in ADU was at 8.07%.
5. The addition of about 2 g NH4NO3 was found to prevent effectively the solution from
precipitating Mg(OH)2 at 5 ml of 25 wt% ammonia water up to 1 g Mg(NO3) ·6H2O.
6. Homogeneous MgyU1-yO2+x solid solutions with y=0.0131, 0.0330 and 0.0807 were
obtained in a single phase by heating the present ADU containing Mg.

25 | Page
2.4.3 Morphology of Precipitate

Manna et al. [30] found that the ADU particle consists of primary platelets, these primary
platelets form primary agglomerates that look like woolen balls or cauliflower and primary
agglomerates are also connected with each other to form secondary agglomerates. Fig. 3
shows the morphology of ADU (obtained at pH 7) using high resolution Scanning Electron
Microscope’ (SEM). It basically consisted of primary platelets of 250-500 nm width and of
500-1000 nm length. In the course of reaction both the size of primary platelets and the
agglomerations increased. It was concluded that microstructure of ADU was retained even
after its calcination to uranium oxides. It was also observed that O/U ratio, bulk density and
tap density of the uranium oxide was reduced with an increase in the calcination temperature.
However, the temperature was not found to have a significant effect on tap density, bulk
density and mean particle size. High resolution SEM revealed that pores were generated
during calcination and at higher temperature sintering of powder took place. As a result
surface area increased with temperature and then reduced after passing through a maximum.

Figure 3: SEM images of final ADU at different magnification a) 500X b) 5000X c) 50000X

The variation of pH of the solution and uranium concentration in the filtrate with time was
also plotted as shown in Fig. 4. It showed that there was a flat zone in the pH curve and most
of the precipitation reaction occurred during the period which is indicated by substantial
decrease in uranium concentration. The same conclusion was drawn from the study of change
in optical density of the samples collected after regular intervals during precipitation.

26 | Page
 Figure 4: Change of pH and uranium concentration in filtrate with time

Doi et al. [31] described that ADU-precipitate consists of very thin elementary platelets of
order of 0.1mm size. In homogeneity in precipitation reaction inevitably leads to
agglomeration of these elementary platelets to much larger particles. Modification of physical
state of ADU-precipitate by precipitation condition is twofold; (1) variation in size of
elementary platelets, (2) variation in agglomerate formation. Calcination of ADU- precipitate
to UO3 and subsequent reduction to UO2 at low temperatures do not involve significant
modification in microstructure of agglomeration introduced by precipitation. On the other
hand, firing the UO3-calcine in hydrogen at elevated temperatures causes extensive sintering
of resulting UO2. Proceeding of this free sintering is markedly affected by the physical state
of very starting ADU-precipitate, since it essentially governs microstructure of UO 2 powder
at early stage of sintering.

2.5 LACUNAE BETWEEN PRESENT SCENARIO AND

PRESENT NEED

No information is available in the published literature regarding the effect of different process
parameters (temperature and flow rate of vapour ammonia), effect of multiple precipitation,

27 | Page
effect of coagulants and different alkali on particle size distribution of the precipitated slurry
to improve filterability and reduce generation of solid active waste.
Therefore, it was thought desirable to undertake a systematic investigation of these
parameters and their impact on particle size distribution and effluent concentration to meet
disposal standards.

28 | Page
Chapter 3
EXPERIMENTS
3.1 EXPERIMENTAL SETUP

UNR precipitation reactor is an agitated 35 liter SS304L reactor with dished bottom.
Schematic drawing and photograph of the precipitator are shown in Fig 5 and 6 respectively.
The reactor is of 350 mm inner diameter and fitted with turbine type of impeller, motor and 4
number equal spacing 25 mm width baffles. Gaseous ammonia (99.9% pure) from ammonia
storage tank is introduced through half circle type sparger. The flow rate of ammonia is
controlled using needle valve and calibrated rotameter. pH and temperature of the solution
were measured using pH electrode and thermometer respectively.

After completion of reaction the slurry was filtered under vacuum using the Rotary Drum
Filter by applying precoat on filter cloth of filter.

The filter aid that is being used by NUOFP(O) is Dicamol 474 for filtration of metallic nitrate
solution. The filter aid is manufactured from naturally occurring amorphous volcanic mineral
of perlite earth composition and has mean particle size of 8 microns. Chemical composition
of Perlite: Element percent- SiO2 - 72%, Al2O3 - 14%, Fe2O3- 0.7%, Na2O -4.0%, K2O - 8.8%,
CaO - 0.3%,MgO - 0.1%,TiO2 - 0.1%.

Vacuum receiving tank is provided to receive the vacuum. Filtrate is collected in a filtrate
collection tank from a vacuum receiving tank.

29 | Page
 Figure 5: Schematic diagram of experimental setup

Figure 6: Experimental setup photograph

30 | Page
3.2 METHODOLOGY OF EXPERIMENTS

1) Carrying out UNR precipitation varying Ammonia flow rates as 0.2m 3/hr, 0.4m3/hr,
0.6m3/hr, 0.8m3/hr and 1m3/hr.

2) Checking/Validating the above experiments by repeating the above experiments once

again

3) Fixing the ammonia flow for which PSD of the UNRC is high and carrying out
precipitation at that ammonia flow by varying temperature as 25deg C, 35deg C, 45deg C,
55deg C & 65deg C.

4) Checking/Validating the above experiments by repeating the above experiments once

again.

5) Fixing the ammonia flow and temperature at the optimised value for studying the effects of
different coagulants.

6) After fixing the coagulant, multiple precipitation experiments will be started.

7) Implementation of findings at the plant scale.

Chapter 4
31 | Page
RESULTS AND DISCUSSION

The four sets of experiments have been performed at 4 different ammonia flow rates 0.4, 0.6,
0.8 and 1 mph.

It has been found that the precipitation time is decreased with increased flow rates as shown
in figure below.
.

Also, it has been found that the particle size distribution decreases with increasing the flow
rate of ammonia.

32 | Page
The flow rate of ammonia is not causing any significant effect on moisture percentage of
Uranyl Nitrate Raffinate Cake.

Ammonium Nitrate correlation with flow rate of ammonia cannot be found out with this
experimental study.

33 | Page
34 | Page
Chapter 5
BIBLIOGRAPHY

1. V. M. Efremenkov(1989),Radioactive waste management at nuclear power plants, IAEA

BULLETIN, 4/1989.
2. Y.S. Kim and H. Zeitlin(1971), Separation of uranium from seawater by adsorbing colloid
flotation, Anal. Chem., 43(11) 1390
3. M. Dulama, M. Iordache, N. Deneanu(2013) ,Treatment of Uranium Contaminated
Wastewater –A Review, Institute for Nuclear Research Pitesti, Romania
4. F. Bunus, Chimie Nucleara, Ed. Stiintifica si enciclopedica, Bucuresti, 1976.
5. H. Sodaye, S. Nisanb, C. Poletikoc, S. Prabhakara, P.K. Tewaria(2009) - Extraction of
uranium from the concentrated brine rejected by integrated nuclear desalination plants
(Desalination 235 (2009) 9–32)
6.
7. C.-K. Yun, Development of a process for continuous extraction of uranium from seawater,
IAEA-R1759-F, 1982
8. H. Sodaye, S. Nisanb, C. Poletikoc, S. Prabhakara, P.K. Tewaria - Extraction of uranium
from the concentrated brine rejected by integrated nuclear desalination plants (Desalination
235 (2009) 9–32)

9. M. Dulama, M. Iordache, N. Deneanu(2013) ,Treatment of Uranium Contaminated

Wastewater –A Review, Institute for Nuclear Research Pitesti, Romania.
10.

11. G. Hsiue, L. Pung, M.Chu, M. Shieh(1989), "Treatment of Uranium Effluent by Reverse

Osmosis Membrane", Desalination, 71, 35

12. M. Chu, C. Tung, M. Shieh (1990), "A Study on Triple-Membrane-Separator (TMS)

Process to Treat Aqueous Effluents Containing Uranium", Separation Science and
Technology, 25, 1339

35 | Page
13. O. Raff, R.D. Wilken(1999), Uranium Removal from Water by Nanofiltration, Mine,
Water&Environment, IMWA Congress, Sevilla, Spain.

14. P. Michard, E. Guibal, , T. Vincent, P. Le Cloirec, Microporous materials, 1996, 5, 309

15 E. Guibal, M. Jansson Charrier, J. Roussy, R. Surjous(1996), P. Le Cloirec, Wat. Sci.
Techn., 34(10),169
16 L. Bengtsson, B. Johansson, T.J. Hackett, L. McHale and A.P. McHale(1995) , Studies on
the biosorption of uranium, Appl. Microbiol. Biotechnol., 45(1995) 807– 811
17 Taichi Sato(1958),The extraction of Uranyl Nitrate from Nitric Acid solutions by Tributyl
Phosphate,Government Chemical Industrial Research Institute, Tokyo Hatagaya, Shibuya-
Ku, Tokyo, Japan
18 P.H. Karpinski and J.S. Wey (2002),Precipitation Processes,Handbook of Industrial
Crystallization (pp.141-160)
19 Hunter, R.J. (1987). Foundations of Colloid Science, vol. 1, Clarendon Press,Oxford,
England.
20 P.H. Karpinski and J.S. Wey (2002),Precipitation Processes,Handbook of Industrial
Crystallization (pp.141-160)
21 A. Acrivos, B. D. Babcock, R. L. Pigford (1959), Chem. Eng. Sci., 10 (1–2), 112.
22 H. W. Cooper(1963), Chem. Eng., 28, 148
23 J. N. Tilton (1999), in Perry’s Chemical Engineers Handbook, 7th ed. (Eds: R. H. Perry,
D. W. Green, J. O. Maloney), McGraw-Hill,New York

24. Stickland AD, White LR, Scales PJ ( 2011). "Models of rotary vacuum drum and disc
filters for flocculated suspensions",AIChE Journal. 57 (4): 951–61.

25 P.V.S.N. Prudhvi Raju , P. Babaji, S. Sairam , D. Mandal (2014),Effect of Free Acidity in

UNPS on quality of ADU powder,CHEMCON-2014,IICHE
26 Narasimha Murthy B, Balakrishna P, Yadav R. B, Ganguly C, Influence of temperature of
precipitation on agglomeration and other powder characteristics of ammonium diuranate,
Powder Technology 115 (2000), 167-183
27. Shrishma Paik, Biswas S, Bhattacharya S, Roy S.B (2013), Effect of ammonium nitrate
on precipitation of Ammonium Di-Uranate (ADU) and its characteristics, Journal of Nuclear
Materials, 440 , 34–38

36 | Page
28. Rajagopal S, Asari T. P. S, Iyer C. S. P, Particle size analysis of ammonium urinate
prepared by conventional and homogeneous methods of precipitation and their corresponding
oxides, Journal of Nuclear Materials, 227 (1996), 300-303.
29. Takeo Fujino, Yoshihide Hoshi, Nobuaki Sato, Kohta Yamada(1999), Wet precipitation
method for mixing magnesium and uranium in preparation of MgyU1-yO2+x solid solution,
Journal of Nuclear Materials, 275 , 19-27.
30. Manna S, Saswati Roy B (2013), Crystal growth and morphological study of ADU and its
calcined product, BARC Newsletter, Founders day special issue, 162-166.
31. Doi H., Ito T. (1964), Significance of physical state of starting precipitates in growth of
uranium dioxide particles, J. Nucl. Mat., 11, , 94-106

37 | Page