The calculation of uncertainty budgets is becoming a standard step in reporting analytical results. This gives rise to the need for simple, easily accessed tools to calculate uncertainty budgets. An example of such a tool is the Excel spreadsheet approach of Robouch et al. Here, we present an internet application which calculates uncertainty budgets for k0-NAA. The Web application has built in Literature values for standard isotopes and accepts as inputs fixed information such as the thermal to epithermal neutron flux ratio, as well as experiment specific data such as the mass of the sample. The application calculates and displays intermediate uncertainties as well as the final combined uncertainty of the element concentration in the sample. The interface only requires access to a standard browser and is thus easily accessible to researchers and laboratories. This may facilitate and standardize the calculation of k0-NAA uncertainty budgets.
A series of reference materials intended for use as activation or fission monitors for neutron fluence rate measurements has been prepared by the Joint Research Centre of the European Commission. Certification has been carried out by expert European laboratories and distribution of the certified reference materials (CRMs) is through the BCR programme of the Commission. The list (18 CRMs) includes materials to cover the complete energy spectrum, and suitable for different irradiation times. Fission monitors are 238UO2 or 237NpO2 in the form of microspheres. Activation monitors are high purity metals (Ni, Cu, Al, Fe, Nb, Rh, or Ti), certified for interfering trace impurities, or dilute aluminium-based alloys, where aluminium is chosen as a suitable matrix for reducing the neutron self-shielding effect. Newly certified materials are IRMM-530R Al-0.1%Au, replacing the exhausted IRMM-530 material, used as comparator for k0-standardization, and three new Al-Co alloys (0.01-1%Co). Two others, in the process of certification are Al-0.1%Ag and Al-2%Sc for thermal and epithermal fluence rate measurements. Other candidate reference materials currently being certified are two uranium-doped glass intended for dosimetry by the fission-track technique.
Authors:P. Vermaercke, P. Robouch, L. Sneyers, and F. De Corte
The thermal to epithermal neutron flux ratio (f) and the deviation of the epithermal neutron spectrum from the 1/E shape (α) are essential parameters for the correct application of k0-standardized neutron activation analysis. Several methods are applied for the determination of f and α. They are based on Cd-covered multi-monitor or on bare-irradiations methods. The recently developed and characterized synthetic
multi-element standards (SMELS) were designed as a validation tool for the proper implementation of the k0-NAA method in a laboratory. In particular, SMELS Type III contains Au and Zr, thus allowing the direct determination of f and α. It could, therefore, replace the traditional flux monitors. Furthermore, it could be used as a quality control material
to monitor the stability of the irradiation facility and the detector. This paper presents the accuracy of the f and α determination and the feasibility of quality control using SMELS for irradiation channel Y4 of the BR1 reactor.
Authors:P. Grant, P. Robouch, R. Torres, and R. Silva
Instrumentation has been developed to perform uv-vis-nir absorbance measurements remotely and at elevated temperatures and pressures. Fiber-optic spectroscopy permits the interrogation of radioactive species within a glovebox enclosure at temperatures ranging from ambient to >100 °C. Spectral shifts as a function of metal-ligand coordination are used to compute thermodynamic free energies of reaction by matrix regression analysis. Pr3+ serves as a convenient analog for trivalent actinides without attendant radioactivity hazards, and recent results obtained from 20–95 °C with the Pr-acetate complexation system are presented. Preliminary experimentation on Am(III) hydrolysis is also described.
Authors:S. Pommé, F. Hardeman, N. Etxebarria, and P. Robouch
A spreadsheet application is developed for the prediction and optimization of the analytical performance of instrumental neutron activation analysis for matrices of more or less known composition. It assists in feasibility testing, sensivitity enhancement and cost reduction.
Authors:S. Pommé, P. Robouch, G. Arana, M. Eguskiza, and M. Maguregui
The boundary conditions in which Poisson statistics can be applied in nuclear spectrometry are investigated. Improved formulas for the uncertainty of nuclear counting with deadtime and pulse pileup are presented. A comparison is made between the expected statistical uncertainty for loss-free counting, fixed live-time and fixed real-time measurements.
Authors:G. Arana, U. Wätjen, C. Ingelbrecht, and P. Robouch
Five copper alloys were prepared with modern powder metallurgical processes in the frame of the European project Improvement of Means of Measurement on Archaeological Copper-Alloys for Characterisation and Conservation (IMMACO) and certified for As, Pb, Sn and Zn mass fractions. Similar in their composition to archaeological bronze alloys, these Certified Reference Materials (CRMs) are to be used for calibration of XRF instruments for characterization of archaeological samples either in the laboratory or in the field. This paper presents and compares the successful contribution of our non-destructive analytical methods (k0-NAA and PIXE) to the IMMACO project and to the certification of the five reference materials.
Authors:M. Eguskiza, P. Robouch, U. Wätjen, and F. De Corte
Three new synthetic multi-element standards (SMELS) were developed for testing the performance of the k0-standardization neutron activation analysis (k0-NAA) method when implemented in a laboratory. SMELS consist of a phenol-formaldehyde polymer matrix spiked with different groups of elements according to the half-lives of the formed radionuclides. They are classified as Type I for short-, Type II for medium- and Type III for long-lived radionuclides. This article presents the preparation of SMELS including different aspects such as choice of the matrix and spiking elements, chemical compounds, target concentrations, purity of the matrix and spiking procedure and the homogeneity study for all the spiked elements in order to demonstrate the quality of the produced materials.
Authors:J. Kučera, M. Eguskiza, F. De Corte, and P. Robouch
Radiation stability of a set of three synthetic multielement standards (SMELS) designed for validation of k0-standardization in neutron activation analysis was tested by monitoring mass and element content changes following irradiation at a high neutron fluence rate (up to 9.1013 n.cm-2.s-1) for stepwise increased periods of time. No mass changes were detected and for all the 26 elements investigated only a chlorine content loss was observed. Thus, radiation stability of the SMELS materials for the given purpose and their suitability for use also in high-power reactors was demonstrated.
Authors:P. Robouch, G. Arana, M. Eguskiza, S. Pommé, and N. Etxebarria
The concepts of the Guide to the expression of Uncertainties in Measurements for chemical measurements (GUM) and the recommendations of the Eurachem document "Quantifying Uncertainty in Analytical Methods" are applied to set up the uncertainty budget for k0-NAA. The "universally applicable spreadsheet technique", described by Kragten, is applied to the k0-NAA basic equations for the computation of uncertainties. The variance components — individual standard uncertainties — highlight the contribution and the importance of the different parameters to be taken into account.