Element flux, measurement methods

The atom flux sputtered from a solid surface under energetic ion bombardment provides a representative sampling of the solid. Sputtered neutral mass spectrometry has been developed as method to quantitatively measure the composition of this atom flux and thus the composition of the sputtered material. The measurement of ionized sputtered neutrals has been a significant improvement over the use of sputtered ions as a measure of flux composition (the process called SIMS), since sputtered ion yields are seriously affected by matrix composition. Neutral panicles are ionized by a separate process after sputter atomization, and SNMS quantitation is thus independent of the matrix. Also, since the sputtering and ionization processes are separate, an ionization process can be selected that provides relatively uniform yields for essentially all elements. 

It should be noted that in a vapour phase the liquid layer on the surface of a sensitive element of the sensor (zinc oxide) must be sufficiently thin, so that it would not produce any influence on the diffusion flux of oxygen through this layer. Possible lack of the film continuity (the presence of voids) does not prevent determination of concentration of oxygen in the bulk of the cell by the vapour - gas method. In this case, one deals with a semi-dry method. On the contrary, the presence of a thick liquid layer causes considerable errors in measuring t, because of different distribution of oxygen in a system gas - liquid layer -semiconductor film (this distribution is close to that in the system semiconductor film - liquid), in addition to substantial slowing down of oxygen diffusion in such systems. 

Sources of weak intensity have fluxes of a few million neutrons per second. They can be used to measure about 20 elements. A variation of this method consists of using a few pg of 252Cf (r = 2.6 years) as a rapid source of neutrons (2 MeV) that are slowed by collision with hydrogen atoms (2.4 x 106 neutrons s"1 pg 1). 

In the activation method an element undergoes nuclear reactions by means of some source producing sufficiently high thermal neutron flux( preferably by a nuclear reactor) to yield radioactive isotopes. These isotopes are usually unstable and return to their ground state by releasing energy in the form of emitted radiations. By measuring these radiations it is possible to identify, in most cases, one or several components in a mixt. Such nuclear transitions are not affected by the state... 

Neutron Activation Spectrometry. Another instrumental technique which has applicability to a wide range of elements is neutron activation analysis. In this method the sample (which could be orange juice without any prior sample treatment) is irradiated with a strong neutron flux. The elements of analytical interest are thus converted to unstable isotopes which decay with characteristic energies and thus measurement of the intensities results in analytical values for the elements of interest. There are some serious drawbacks to this method, however. The matrix can cause severe background effects especially when the sample contains large amounts of an element, like potassium, which is the situation with orange juice. In this event tedious chemical separations must be carried out to achieve adequate selectivity, accuracy... 

There is also a standard test method for determination of major and minor elements in coal ash by inductively coupled plasma (ICP)-atomic emission spectrometry (ASTM D-6349). In the test method, the sample to be analyzed is ashed under standard conditions and ignited to constant weight. The ash is fused with a fluxing agent followed by dissolution of the melt in dilute acid solution. Alternatively, the ash is digested in a mixture of hydrofluoric, nitric, and hydrochloric acids. The solution is analyzed by (ICP)-atomic emission spectrometry for the elements. The basis of the method is the measurement of atomic emissions. Aqueous solutions of the samples are nebulized, and a portion of the aerosol that is produced is transported to the plasma torch, where excitation and emission occurs. Characteristic line emission spectra are produced by a radio-frequency inductively coupled plasma. A grating monochromator system is used to separate the emission lines, and the intensities of the lines are monitored by photomultiplier tube or photodiode array detection. The photocurrents from the detector... 

An attractive method to produce single crystals (in the dimension range from pm to several nun) is the high-temperature solution (flux) method, becanse of its simphcity and the low temperature required. The elements are dissolved in the solvent metal (often Al) and subseqnently the solntion is slowly cooled to room temperature. A prerequisite is, of course, that the solubility of the used solvent in the desired boride is insignificant. The solubility of Al in most boron-rich binary borides has been found to be extremely small. Crystals prepared in this manner are suitable for measurement of physical properties, for instance, microhardness, electrical resistivity, and so on. 

With elements of short half-life, the sensitivity of the method, besides being dependent on the flux and activation cross section, will also depend on the time which must elapse between the termination of activation and the measurement of the activity. With short-lived nuclides this period frequently determines the over-all sensitivity of the method. 

XRF is one of the standard techniques used for the analysis of the elemental composition of zeolites. However, normally sample preparation is rather complicated, involving the preparation of the zeolite in a ceramic flux or in other matrices in order to have a standard sample geometry and size which is a requirement for precise analysis. This kind of sample preparation is not possible if the analysis is to be performed in high-throughput mode. An alternative method to conventional XRF makes use of focussing the X-ray radiation as in the case of diffraction, however, not the diffracted X-rays are collected, but the element specific fluorescence. Since the matrices and the sample geometries are rather ill-defined in this measurement mode, analysis is more of a semiquantitative character than quantitative. Nevertheless, for screening purposes this is a quite valuable method. 

The availability of high flux thermal neutron irradiation facilities and high resolution intrinsic Ge and lithium drifted germanium (Ge(Li)) or silicon (Si(Li)) detectors has made neutron activation a very attractive tool for determining trace elemental composition of petroleum and petroleum products. This analytical technique is generally referred to as instrumental neutron activation analysis (INAA) to distinguish it from neutron activation followed by radiochemical separations. INAA can be used as a multi-elemental method with high sensitivity for many trace elements (Table 3.IV), and it has been applied to various petroleum materials in recent years (45-55). In some instances as many as 30 trace elements have been identified and measured in crude oils by this technique (56, 57). 

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