Uday Kumar Thakur

Fluoride determination in various matrices relevant to nuclear industry : A review

The determination of fluoride from diverse matrices at front and back end of nuclear technology and some studies from this laboratory on optimizations of different experimental parameters differing with multiple fuels and reactor materials, have been reviewed. The most useful techniques such as fluoride ion selective electrode (F-ISE) and ion-chromatography (IC) widely adopted as routine methods for fluoride determination in nuclear industry have been discussed. The effect of various buffer strengths on the response of the fluoride ion selective electrode has been examined. The ion chromatographic studies on mobile phase concentration, medium of sample, sample injection volume etc. to get distinct fluoride peak within optimum time in presence of other anionic species in diverse concentrations have been reported. The results of various sample matrices such as UO2, PuO2, (U,Pu)O2, Pu-alloy, thoria, zircaloy, slag, HLLW, LLLW etc., analyzed after matrix separation using pyrohydrolysis setup, for both solid and liquid samples and without matrix separation by masking potentially interfering ions of liquid samples, have been presented.

Studies on protonation and Th(IV) complexation behaviour of dihydroxybenzenes in aqueous 1 M NaClO4 medium

Complexing behaviour of three dihydroxybenzenes (DHB) namely, hydroquinone, resorcinol and catechol with Th(IV) along with their protonation constants were studied in 1 M NaClO4 medium at 23 ± 0.5 °C, using pH titration technique. Both protonation and metal-ligand equilibrium constants of dihydroxybenzenes were computed using advance software suite of program HYPERQUAD. Logarithmic values of overall protonation constants (log β1H and log β2H) were found to be 11.47 ± 0.05 and 21.45 ± 0.06, for hydroquinone, 11.76 ± 0.04 and 20.98 ± 0.04 for resorcinol and 12.58 ± 0.03 and 21.87 ± 0.08 for catechol respectively. Complex formation has been investigated in the pH range 2 to 4. The logarithmic values of metal-ligand equilibrium constants obtained in the present work were β13-1=48.51 ± 0.67 and β14-1=64.86 ± 1.25 for hydroquinone, β110=16.98 ± 0.16, β13-1=46.46 ± 0.18 and β14-2=59.65 ± 0.20 for resorcinol and β11-1=14.06 ± 0.10 for catechol. The literature values were reviewed.

Separation of Boron from Borated Paraffin Wax by Pyrohydrolysis and Alkali Extraction Methods and Its Determination Using Ion Chromatography

A method based on the pyrohydrolysis extraction of boron and its quantification with ion chromatography was proposed for paraffin waxes borated with H3BO3 and B4C. The optimum pyrohydrolysis conditions were identified. Wax samples were mixed with U3O8, which prevents the sample from flare up, and also accelerates the extraction of boron. Pyrohydrolysis was carried out with moist O2 at 950°C for 60 and 90 min for wax with H3BO3 and wax with B4C, respectively. Two simple methods of separation based on alkali extraction and melting wax in alkali were also developed exclusively for wax with H3BO3. In all the separations, the recovery of B was above 98%. During IC separation, B was separated as boron-mannitol anion complex. Linear calibration was obtained it between 0.1 and 50 ppm of B, and LOD was calculated as 5 ppb (S/N = 3). The reproducibility was better than 5% (RSD).

Studies on U-Zr and U-Pu-Zr alloys for determination of Cl and F using pyrohydrolysis

Abstract Pyrohydrolysis method was studied for the separation of Cl and F from U-Zr and U-Pu-Zr alloy nuclear fuels and determination by ion chromatography. A detailed study was performed on pyrohydrolysed products of U-Zr alloy, obtained on heating in moist argon and oxygen atmospheres using X-ray powder diffraction (XRD) and thermogravimtric methods. Using oxygen as the carrier gas pyrohydrolysis performed at 900 ℃ was complete within 30 min. It was found that, moist oxygen as carrier gas only could open the matrix completely within stipulated time. This was attributed to the formation of α-U3O8, which was not possible in moist argon heating for 30 min. The pyrohydrolysis in moist Ar required 60–90 min for complete removal of halides. The method was then successfully extrapolated to U-Pu-Zr alloys. The results showed recovery up to 90% or above for the optimized conditions.

Direct Separation of Molybdenum from Solid Uranium Matrices Employing Pyrohydrolysis, a Green Separation Method, and Its Determination by Ion Chromatography.

Pyrohydrolysis is a well-established separation method, and it is being used as a sample preparation method for several materials for further determination of non-metals such as halogens, boron, and sulfur. Analytes are retained in a diluted solution that is suitable for carrying out analysis by several determination techniques and minimizing the use of concentrated reagents. Pyrohydrolysis separation of metals has not been reported yet. The present study demonstrates the pyrohydrolysis separation of Mo as MoO4(2-) from uranium materials and its subsequent determination using ion chromatography coupled with suppressed conductivity detector. With use of TGA and XRD the volatilization behavior of Mo was studied. Important parameters for the pyrohydrolysis method required for the quantitative separation of Mo were evaluated. The precision of the method was better than 5% at 25 ppm of Mo. The accuracy was evaluated by analysis of a CRM (U3O8-ILCE-IV). The method was applied to determine Mo in ammonium diuranate samples, where the conventional methods suffer from the loss of Mo.