Mixed oxide (MOX) fuel is an alternative to conventional enriched uranium oxide fuel in thermal reactors. Indian interest
in plutonium recycle in thermal reactors is primarily due to the need to develop alternative indigenous fuel for two boiling
water reactors (BWR) at Tarapur, which are designed to use imported light enriched uranium fuel. A few MOX assemblies have
been fabricated and loaded into the reactors. Neutron well coincidence counting (NWCC) system has been successfully employed
to check the enrichments of PuO2 in MOX blends. NWCC has also been successfully applied in developing dry recycling process of clean rejected oxide (CRO)
and dirty rejected oxide (DRO).
Authors:Pradeep Kumar, Dipti Shah, and K. Ramakumar
Correlations have been established between %Eff 240Pu and various plutonium isotopes formed in thermal reactors. Based on these correlations, a method has been developed for
the estimation of isotopic composition of plutonium obtained from thermal reactors. The method is simple, fast, non-destructive
and finds application for the verification of plutonium isotopic composition in the finished products of known plutonium content.
The method could be applied in the nuclear fuel fabrication to verify and confirm the fissile content (239Pu+241Pu) specification. It has also been shown that in principle, similar correlations could be established for Pu obtained from
different thermal reactor fuels with reactor specific fitting parameters.
Determinations of hexamethylene tetramine (HMTA) and urea in the process solutions are required to optimize their concentrations for obtaining high quality ceramic oxide microspheres, for monitoring the washing procedure and for their subsequent recovery, recycling or waste disposal. Determination of urea in the feed solution by conventional procedures is difficult as it contains HMTA. It is more so in the effluent as it contains hydrolytic products like formaldehyde, methylol derivatives of urea, ammonium nitrate and ammonium hydroxide used for washing the gel microspheres. This work describes a derivative potentiometric method using a microprocessor-based autotitrator. Peaks on the first derivative of the titration plot corresponded to constituents of different basicities. Urea was selectively hydrolyzed at room temperature by the catalytic action of urease enzyme leaving HMTA unaffected. Ammonium hydroxide and ammonium bicarbonate produced from urea and HMTA were sequentially titrated for the analysis of the feed solution to obtain the three corresponding peaks respectively. Two separate titrations were required for the analysis of the effluent solution, which contained free ammonia also. One aliquot was first titrated directly without adding urease (for free ammonia and HMTA) and another aliquot was titrated after treatment with urease. The end points due to the ammonia used for washing and that from urea hydrolysis merged resulting in the appearance of three peaks again. Using this sequential method the relative standard deviations were found to be 0.81% and 1.38% for urea and HMTA, respectively, in eight determinations when the aliquots contained 50 to 75 mg of urea and 75 to 125 mg of HMTA. Feed and effluent solutions of the process stream were analyzed.
Authors:Ankita Rao, Pradeep Kumar, and K. Ramakumar
Uranium from different uranium oxide matrices was extracted with tri-n-butyl phosphate–nitric acid (TBP–HNO3) adduct using supercritical carbon dioxide (SC CO2). While 30 min dissolution time at 323 K was sufficient for U3O8 and UO2 powder, UO2 granule (at 333 K) and crushed green pellet (at 353 K) required 40 min. Crushed sintered pellet required 60 min at 353 K
for complete dissolution. Influence of various experimental parameters such as temperature, pressure, volume of TBP–HNO3 adduct, acidity of nitric acid used for preparing TBP–HNO3 adduct and extraction time on uranium extraction efficiency was also investigated. For UO2 powder, temperature of 323 K, pressure of 15.2 MPa, 1 mL TBP–HNO3 adduct, 10 M nitric acid and 30 min extraction time was found to be optimum. ~70% uranium extraction efficiency was obtained
on extraction with SC CO2 alone which increased to 90% with the addition of 2.5% TBP in SC CO2 stream. Extraction efficiency was found to vary linearly with TBP percentage and nearly complete uranium extraction (~99%)
was observed with 20% TBP. Nearly complete extraction was also achieved with addition of 2.5% thenoyltrifluoroacetylacetone
(TTA) in methanol. The optimized procedure was extended to remove uranium from simulated tissue paper waste matrix smeared
with uranium oxide solids.
Experimental evaluation of the procedures adopted for heat capacity measurements employing differential scanning calorimetry
(DSC) has been carried out by taking nickel and sapphire as test samples. Among the various methodologies reported in literature,
the absolute dual step method was chosen for this purpose due to its simplicity and minimum number of measurements required.
By proper temperature and heat flux calibration employing indium as reference, it was possible to obtain the calibration factor
independent of temperature. This was ascertained by analysing other pure metals namely Sn, Zn, Cd, and Pb and determining
their melting temperatures and heats of melting. Various operator- and sample-dependent parameters such as heating rate, sample
mass, the structure of the sample, reproducibility and repeatability in the measurements were investigated. Heat capacities
of both nickel and sapphire have been determined using the above method. Further, the heat capacity of nickel has also been
using the widely employed three-step method taking sapphire as the heat flux calibration standard. Both methods yielded the
comparable heat capacity values for nickel. Based on the parameters investigated and their influence, it could be concluded
that reasonably precise and accurate heat capacity measurements are possible with DSC. One advantage of this method is the
elimination of a separate calibration run using a reference material of known heat capacity.
Authors:K. Tirumalesh, K. Ramakumar, S. Chidambaram, S. Pethaperumal, and Gursharan Singh
Concentrations of five rare earth elements (REE) were measured in clay samples of a deep bore hole comprising major aquifers
of Pondicherry region, south India in order to investigate the geochemical variations among various litho-units. Clay samples
from Cretaceous formation show distinct gray to black color whereas Tertiary deposits have clays with color varying from pale
yellow to brown to gray. All measured REEs exhibit lower concentrations than Upper Continental Crust (UCC) average values.
Large variations in REEs contents were observed in different sedimentary formations (Tertiary and Cretaceous). Chondrite normalized
ratio of La/Lu and Eu/Eu* indicate that the clays are derived from weathering of felsic rock and possibly under humid climate.
All the samples showed positive Eu anomaly in North American Shale Composite (NASC) normalized plot which shows plagioclase
feldspar as the major contributor to these clays. Positive Eu anomaly is also an indication of reduced condition of the formation.
Authors:K. Ramakumar, V. Raman, V. Sant, V. Kavimandan, and H. Jain
Determination of trace impurities in zircaloy-2 and tellurium by Spark Source Mass Spectrometry (SSMS) is reported. The advantage of SSMS lies in the fact that along with metallic trace constituents even the nonmetallic impurities and gases including hydrogen can also be determined.
Authors:P. Kalsi, B. Tomar, K. Ramakumar, and V. Venugopal
Application of power ultrasound in chemical processes is recognized as an effective tool to solve many industrial problems
encountered in processes involved in nuclear industry, particularly, digestion and leaching steps. In addition, problems related
to radiological safety are the most important factors to be considered, when handling radioactive materials. Sonochemical
processes, due to relatively low temperature operations, are attractive in this regards. Further they are eco-friendly and
economical as well. Hence, sonochemical studies were taken up for the removal of uranium from fluoride containing matrix.
Dissolution studies were carried out in nitric acid medium, in a 5 L capacity tank type sono-reactor, operating at frequency
and power of 22 ± 3 kHz and 150 W respectively. The parameters studied were concentration of HNO3, temperature of water-bath, choice of purged gas (air/oxygen) and flow rate of purged gas passed. Experiments were also carried
out to study the amount of fluoride matrix dissolved. Enhancement with US was 76 to 91 % for U removal from MgF2 slag in 2 M HNO3. The prime advantage achieved is the reduction in the reaction time. Other advantages are minimizing labor, remotisation
of operations to reduce radiation exposure, use of less acid and accordingly lesser effluent for treatment before disposal.
Authors:R. Sawant, R. Sharma, N. Chaudhuri, and K. Ramakumar
The hydrolytic behavior of thorium(IV) and dioxo-uranium(VI) was studied in the absence as well as in the presence of small concentration of fluoride in the pH range of 2.0 to 4.0 and 2.0 to 5.5, respectively. Effects of metal ion concentration and time dependence of the hydrolytic process were also investigated. The log values of
13* computed from the best model of species distribution were found to be -3.51±0.03, and -10.75±0.14 for thorium(IV). Similarly, the best model for dioxo-uranium consisted of
47* species having values -6.15±0.05-18.43±0.09 and -23.36±0.07, respectively. Recently developed HYPERQUAD computer program was used for analyzing the various aspects of solution equilibrium species. Different models of chemically possible species distribution were invoked to identify the best model for which HYPERQUAD yields the best fitting of experimental data with least errors. The best model was also decided on the basis of chemical feasibility of the reaction. The species distribution of hydrolytic product remained unaffected in the presence of small quantity of fluoride ions (~1% of thorium and uranium concentration). Moreover, fluoride was found to be helpful in suppressing the early polymerization and colloid formation at the metal ion concentrations investigated. The small amounts of fluoride did not seem to affect the response of glass electrode significantly. The formations of fluoride containing ternary complexes were also not observed at 1% fluoride concentration.
Authors:R. Sawant, Poonam Verma, H. Mhatre, N. Chaudhuri, and K. Ramakumar
The stability constants of the aqueous mono-fluoride complexes of Pu(III) and Am(III) have been measured using the distribution method. A correlation of the available stability constants of fluoride complexes of trivalent actinides, up to Cf, with fundamental properties like charge and radii of the metal ion has been discussed. Good correlation within the group and as a part of other metal ions was obtained only for transplutonium elements. The reported stability constant values measured by potentiometry and the value obtained by distribution for Pu3+ appear to be much higher than expected from this correlation. However, a better correlation was obtained with transplutonium elements when effective charge instead of formal charge was considered for Pu3+ in the BSE function.