Determination of trace amounts of nitrogen in uranium based samples by ion chromatography (IC) without Kjeldahl distillation

A simple, sensitive and fast ion chromatographic (IC) method with suppressed conductivity detection is described for the determination of traces of nitrogen in uranium based fuel materials. Initially a method was developed to determine nitrogen as NH₄⁺ using cation exchange column after matrix separation by Kjeldahl distillation. The method was then improved by eliminating this distillation. Matrix separation after sample dissolution was done by hydrolyzing and filtering off the polyvalent cations. This had helped in reducing both the sample size and analysis time. Optimization of dissolution conditions for various kinds of uranium based samples was done to keep acid content minimum; a prerequisite chromatographic condition. The calibration plot for nitrogen was linear in the concentration range of 0.02-1 mg L⁻¹ with regression coefficient of 0.9999. The relative standard deviation (R.S.D.) obtained in this method (100 μL injected) was 3% and 2% in 9 replicates at nitrogen level of 28 and 55 ng g⁻¹, respectively. Detection limit based on S/N = 3 (100 μL injected) as well as three times of variation in blank value was 4 ng g⁻¹. The developed method was authenticated by comparison with certified uranium-alloy standard as well as with independent indophenol photometry method. The developed method was applied to uranium-alloy, uranium-metal, sintered UO₂ pellets and sintered UO₂ microspheres samples.     

Relative sensitivity factors for the determination of rare earth elements in uranium oxide by Spark Source Mass Spectrometry

Summary Relative Sensitivity Factors (RSFs) for the rare earth elements Ce, Nd, Sm, Eu, Gd, Dy, Er and Lu in U₃O₈ have been determined by Spark Source Mass Spectrometry (SSMS) using the electrical detection system in peak switching mode. Earlier RSFs for these elements were determined in uranyl nitrate and it was expected that though the absolute value of the RSFs may be different, the trend would be the same. However, the present work shows that apart from the magnitude, the trend in RSF values is also different. The data from the present work are in agreement with the theoretical calculations based on the decomposition energies of the rare earth oxides and support the work carried out by others in the case of Y₂O₃ matrix.

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Relative Empfindlichkeitsfaktoren für die Bestimmung Seltener Erden in Uranoxid mit Hilfe der Funken-Massenspektrometrie

Zusammenfassung Die relativen Empfindlichkeitsfaktoren für die Elemente Ce, Nd, Sm, Eu, Gd, Dy, Er und Lu in U₃O₈ wurden mit der Funken-Massenspektrometrie mit elektrischem Nachweis (peak switching) bestimmt. Früher sind diese Faktoren in Uranylnitrat bestimmt worden und es wurde erwartet, daß trotz unterschiedlicher absoluter Werte der Trend derselbe wäre. Es zeigte sich jedoch, daß auch der Trend verschieden ist. Die Werte der vorliegenden Untersuchung stimmen mit theoretischen Berechnungen aus den Zersetzungsenergien der Seltenerdoxide überein und bestätigen die Ergebnisse anderer Autoren für die Y₂O₃-Matrix.

     

Separation behavior of U(VI) and Th(IV) on a cation exchange column using 2,6-pyridine dicarboxylic acid as a complexing agent and its application for the rapid separation and determination of U and Th by ion chromatography

The retention behavior of U and Th as their 2,6-pyridine dicarboxylic acid (PDCA) complexes on a cation exchange column was investigated under low pH conditions. Based on the observed retention characteristics, an ion chromatographic method for the rapid separation of uranium and thorium in isocratic elution mode using 0.08 mM PDCA and 0.24 M KNO(3) in 0.22 M HNO(3) as the eluent was developed. Both uranium and thorium were eluted as their PDCA complexes within 2 min, whereas the transition and lanthanide metal cations were eluted as an unresolved broad peak after thorium. Under the optimized conditions both U and Th have no interference either from alkali and alkaline earth elements up to a concentration ratio of 1:500 or from other elements up to 1:100. The detection limits (LOD) of U and Th were calculated as 0.04 and 0.06 ppm, respectively (S/N=3). The precision in the measurement of peak area of 0.5 ppm of both U and Th was better than 5% and a linear calibration in the concentration range of 0.25-25 ppm of U and Th was obtained. The method was successfully applied to determine U and Th in effluent water samples.     

Determination of alkali and alkaline earth elements along with nitrogen in uranium based nuclear fuel materials by ion chromatography (IC)

An accurate and sensitive ion chromatographic (IC) method with suppressed conductivity detection is described for determination of traces of Na, K, Mg and Ca along with nitrogen in uranium based materials. The method involves matrix separation after sample dissolution by hydrolyzing and filtering off the polyvalent cations. Transition elements interfering in the determination of Ca were removed by cation exchange cartridge containing iminodiacetate resin. Detection limits were between 2 and 6 μg L⁻¹ and overall precision were better than ±5%. Recovery of spiked cations was in range from 96% to 104%. Results obtained were in good agreement with other methods.     

Determination of total gas content and its composition in Indian PFBR blanket pellets

Total gas content and its composition are important specifications for sintered nuclear fuel pellets particularly in the case of fast breeder reactor fuels. Most commonly, total gas content and its composition is determined by hot vacuum extraction-quadrupole mass spectrometry (HVE-QMS). A number of parameters in this methodology such as temperature, duration of heating for quantitative extraction of evolved gases, total volume of the system, gas analysis conditions etc. need to be optimized for reliable measurements. In addition, sensitivity factors for various gases like H₂, CH₄, N₂, CO, O₂ and CO₂ in quadrupole mass spectrometry required for quantification of results have been determined and validated employing reference gas mixtures of known composition. Employing these optimized conditions total gas content and its composition in blanket pellets (uranium oxide pellets) of Indian prototype fast breeder reactor was determined employing HVE-QMS. The relative expanded uncertainty (at a coverage factor k = 2) in the measurement of total gas content excluding hydrogen was estimated as per ISO guidelines and it was found to be 9.2 %.     

Synthesis of garnet structured Li7+x La3Y x Zr2-x O12 (x = 0–0.4) by modified sol–gel method

Preparation of lithium garnet Li₇La₃Zr₂O₁₂ (LLZ) in cubic phase by solid state method requires high temperature sintering around 1,200 °C for 36 h in Al₂O₃ crucible with intermittent grinding. Synthesis of LLZ in cubic phase at lower temperatures by wet chemical methods was reported earlier, however that decompose at high temperature around 850 °C. In this work we report the systematic studies on synthesis of garnet structured electrolytes by modified sol–gel method by the simultaneous substitution of Li⁺ and Y³⁺ for Zr⁴⁺ according to the formulae Li_7+x La₃Y _x Zr_2-x O₁₂ (x = 0, 0.1, 0.2, 0.3 and 0.4). The present investigation revealed that the cubic garnet phase is obtained at much lower temperature for Li₇La₃Zr₂O₁₂ and the simultaneous increase of both Li⁺ and Y³⁺ in Li_7+x La₃Y _x Zr_2-x O₁₂ requires slightly higher sintering temperatures for the formation of cubic garnet phase. SEM micrographs of the Li_7+x La₃Y _x Zr_2-x O₁₂ (x = 0, 0.1, 0.2, 0.3 and 0.4) annealed at minimum sintering temperature required for the formation of cubic garnet phase revealed the increase in grain size and relatively dense structure with increase of x in Li_7+x La₃Y _x Zr_2-x O₁₂.     

Sequential determination of urea and HMTA in the process solution of sol-gel route of advanced nuclear fuel fabrication

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.