Nuclear Neutron Activation

Abstract. The applications of rare earth elements (REE) in various technological fields are reviewed, with emphasis on the importance of the knowledge of the chemical composition of the materials used. Nuclear neutron activation (NNA), atomic absorption spectrometry (AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), inductively coupled plasma-mass spectrometry (ICP-MS) and x ray fiuorescence spectrometry (XRF) are the most frequently used analytical techniques for determining REE. Complex matrices require the prior separation of the analytes by column chromatography. 

Leaving historic antecedents aside, the following sections discuss the determination of REE by instrumental techniques including nuclear neutron activation, atomic absorption spectrometry, plasma spectrometries and x ray fluorescence spectrometry. In combination, these techniques account for over 90% of all analyses for REE. 

Neutron Activation Analysis Few samples of interest are naturally radioactive. For many elements, however, radioactivity may be induced by irradiating the sample with neutrons in a process called neutron activation analysis (NAA). The radioactive element formed by neutron activation decays to a stable isotope by emitting gamma rays and, if necessary, other nuclear particles. The rate of gamma-ray emission is proportional to the analyte s initial concentration in the sample. For example, when a sample containing nonradioactive 13AI is placed in a nuclear reactor and irradiated with neutrons, the following nuclear reaction results. 

The concentration of Mn in steel can be determined by a neutron activation analysis using the method of external standards. A 1.000-g sample of an unknown steel sample and a 0.950-g sample of a standard steel known to contain 0.463% w/w Mn, are irradiated with neutrons in a nuclear reactor for 10 h. After a 40-min cooling period, the activities for gamma-ray emission were found to be 2542 cpm (counts per minute) for the unknown and 1984 cpm for the standard. What is the %w/w Mn in the unknown steel sample ... 

MetaUic impurities in beryUium metal were formerly determined by d-c arc emission spectrography, foUowing dissolution of the sample in sulfuric acid and calcination to the oxide (16) and this technique is stUl used to determine less common trace elements in nuclear-grade beryUium. However, the common metallic impurities are more conveniently and accurately determined by d-c plasma emission spectrometry, foUowing dissolution of the sample in a hydrochloric—nitric—hydrofluoric acid mixture. Thermal neutron activation analysis has been used to complement d-c plasma and d-c arc emission spectrometry in the analysis of nuclear-grade beryUium. 

All the techniques discussed here involve the atomic nucleus. Three use neutrons, generated either in nuclear reactors or very high energy proton ajccelerators (spallation sources), as the probe beam. They are Neutron Diffraction, Neutron Reflectivity, NR, and Neutron Activation Analysis, NAA. The fourth. Nuclear Reaction Analysis, NRA, uses charged particles from an ion accelerator to produce nuclear reactions. The nature and energy of the resulting products identify the atoms present. Since NRA is performed in RBS apparatus, it could have been included in Chapter 9. We include it here instead because nuclear reactions are involved. 

The neutron activation technique mentioned in the preceding paragraph is only one of a range of nuclear methods used in the study of solids - methods which depend on the response of atomic nuclei to radiation or to the emission of radiation by the nuclei. Radioactive isotopes ( tracers ) of course have been used in research ever since von Hevesy s pioneering measurements of diffusion (Section 4.2.2). These techniques have become a field of study in their own right and a number of physics laboratories, as for instance the Second Physical Institute at the University of Gottingen, focus on the development of such techniques. This family of techniques, as applied to the study of condensed matter, is well surveyed in a specialised text... 

Nuclear Data for Elements Analyzed by Neutron Activation . ... 

This can result in a radioactive product from the A(n, t)A reaction where A is the stable element, n is a thermal neutron, A is the radioactive product of one atomic mass unit greater than A, and y is the prompt gamma ray resulting from the reaction. A is usually a beta and/or gamma emitter of reasonably long half-life. Where access to a nuclear reactor has been convenient, thermal neutron activation analysis has proven to be an extremely valuable nondestructive analytical tool and in many cases, the only method for performing specific analyses at high sensitivities... 

The concrete block walls of the cell housing the generator tube and associated components are 1.7 meters thick. The facility also includes a Kaman Nuclear dual-axis rotator assembly for simultaneous transfer and irradiation of reference and unknown sample, and a dual Na iodide (Nal) scintillation detector system designed for simultaneous counting of activated samples. Automatic transfer of samples between load station to the rotator assembly in front of the target, and back to the count station, is accomplished pneumatically by means of two 1.2cm (i.d.) polyethylene tubes which loop down at both ends of the system and pass underneath the concrete shielding thru a pipe duct. Total one-way traverse distance for the samples is approx 9 meters. In performing quantitative analysis for a particular element by neutron activation, the usual approach is to compare the count rates of an unknown sample with that of a reference standard of known compn irradiated under identical conditions... 

For fast neutron activations, the samples were irradiated with a Kaman nuclear neutron generator (Model A711) under conditions similar to those described In this article under the section... 

Neutron activation reactions have also been considered for mine detection. Here a radioactive element is produced in the mine which in the process of decay, emits nuclear radiation, either alpha or beta particles or yrays or two of these or all three in combination. For buried mines the penetrating 7iays are of most in-... 

This section will deal briefly with some aspects of expls safety peculiar to neutron activation analysis expts. We are concerned here with a) the possible effect of the ionizing radiation dose on the energetic material which will cause it to be more sensitive or hazardous to normal handling as an expl, and b) the potential direct expl hazards involved in the physical and mechanical transportation of samples to and horn the irradiation source and in a nuclear counting system... 

The properties of such materials are not measurably altered until subjected to doses in excess of a million rads. At these higher doses, the principal changes are due to chem decompn which, with very few exceptions, resnlt in a decrease in sensitivity to mechanical stimulus and also in a dimunition of expl output. The radiation doses normally encountered in neutron activation procedures range from a few rads for 14 MeV fast neutron activation to several thousand rads for thermal neutron activations in a nuclear reactor. Thus, such doses are well under the limit at which measurable changes can occur... 

A. Harrison, AnalChem 41 (1969), 1396 8) V. Guinn et al, Applications of Neutron Activation Analysis in Scientific Crime Investigations , Gulf General Atomic Corp Rept GA-9807 (1970) 9) K. Pillay et al, Nuclear... 

Eighteen isotopes of sulfur, 17 of selenium, 21 of tellurium, and 27 of polonium have been registered of these, 4 sulfur, 6 selenium, and 8 tellurium isotopes are stable, while there is no stable isotope of polonium. None of the naturally occurring isotopes of Se is radioactive its radioisotopes are by-products of the nuclear reactor and neutron activation technology. The naturally occurring, stable isotopes of S, Se, and Te are included in Table 1.2. 

In addition to the aforementioned methods, TLC in combination with other instrumental techniques have also been used for quantification of inorganic species. For example, two-dimensional TLC coupled with HPLC has been utilized for the separation and quantification of REEs in nuclear fuel fission products using silaiuzed silica gel as layer material [60]. In another interesting method, REEs in geological samples have been determined by ICP-AAS after their preconcentration by TLC on Fixion plates [32]. TLC in combination with neutron activation has been used to determine REE in rock samples on Eixion 50 x 8 layers with the sensitivity limit of 0.5 to 10 pg/g for 10- to 30-mg samples [41]. A combination of TLC and A AS has been utilized for the isolation and determination of zinc in forensic samples [27]. 

Neutron Activation Analysis X-Ray Fluorescence Particle-Induced X-Ray Emission Particle-Induced Nuclear Reaction Analysis Rutherford Backscattering Spectrometry Spark Source Mass Spectrometry Glow Discharge Mass Spectrometry Electron Microprobe Analysis Laser Microprobe Analysis Secondary Ion Mass Analysis Micro-PIXE... 

The EC decay of (ty2 = 140 days), which is produced from by thermal neutron activation in a nuclear reactor, populates the two Mossbauer levels of Ta at excitation energies of 6.2 and 136.2 keV. 

The characteristics of radiochemical methods are well known [435]. An overview of the determination of elements by nuclear analytical methods has appeared [436]. Some selected reviews of nuclear methods of analysis are available charged particle activation analysis [437,438], instrumental neutron activation analysis [439-441] and ion-beam analysis [442]. 

Neutron activation analysis (NAA) is a supreme technique for elemental analysis (Section 8.6.1). Other nuclear analytical techniques, such as PIXE (Section 8.4.2) and RBS, also find application in investigations of diffusion processes [445]. 

Harbottle, G. (1990), Neutron activation analysis in archaelogical chemistry, in Yoshihara, K. (ed.), Chemical Applications of Nuclear Probes, Topics in Current Chemistry, Springer, Berlin, Vol. 157, 57-91. 

Nuclear bombardment reactions in which the product is radioactive constitute the basis of radioactivation analysis (p. 456). Although in principle any bombardment-decay sequence may be used the analyst is largely concerned with thermal neutron activation. Equation (10.13) relates the induced activity to the amount of the parent nucleide (analyte). However, practical difficulties arise because of flux inhomogeneities. It is common therefore to irradiate a standard with very similar characteristics alongside the sample, e.g. for a silicate rock sample a standard solution would be evaporated on to a similar amount of pure silica. On the assumption that identical specific activities for the analyte are then induced in the sample and standard, the amount w2 of analyte is readily calculated from... 

Figure 2.13 Schematic diagram of the nuclear processes involved in neutron activation analysis. Prompt gamma neutron activation analysis (PGNAA) occurs within the reactor delayed gamma NAA (DGNAA) occurs at some remote site. (After Glascock, 1994 Fig. 1. John Wiley Sons Limited. Reproduced with permission.)...

The y particle is emitted virtually instantaneously on the capture of the neutron, and is known as a prompt y - it can be used analytically, in a technique known as prompt gamma neutron activation analysis (PGNAA), but only if such y s can be measured in the reactor during irradiation. Under the conditions normally used it would be lost within the nuclear reactor. In this reaction, no other prompt particle is emitted. The isotope of sodium formed (24Na) is radioactively unstable, decaying by beta emission to the element magnesium (the product nucleus in Figure 2.13), as follows ... 

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