Spectrum Evaluation Techniques

Spectrum evaluation is a crucial step in X-ray analysis, as important as sample preparation and quantification. As with any analytical procedure, the final performance of X-ray analysis is determined by the weakest step in the process. Spectrum evaluation in EDXRF analysis is more critical than in WDXRF spectrometry because of the relatively low resolution of the solid-state detectors employed. 

---

Thermal analysis comprises a spectrum of techniques in which properties of a material are measured as a function of temperature, time, and other variables, while the material is subjected to a controlled temperature program. Analytical techniques include (i) gravimetric-based systems (thermal gravimetric analysis) for evaluation... 

It is seen that exact frequencies shift, depending upon sample state (melt spectrum or KBr pellet) as well as on specific group influence. It is useful to note that the amide I band is specific for constitution since it contributes significantly to the allophanate group absorption and was utilized for evaluating the melt spectrum. This technique is useful, soundly based on literature correlations, but is highly empirical. Trial and error must be used... 

Cross-correlation is used to evaluate the similarity between the spectra of two different systems, for example, a sample spectrum and a reference spectrum. This technique can be used for samples where background fluctuations exceed the spectral differences caused by changes in composition. The cross-correlation technique also can be used to generate the spectra of the pure components from the mixture spectra when the pure component spectra are not available, or when the pure component spectra differ significantly from the isolated pure spectra because of interaction or matrix effects. 

The different techniques of NDT were applied to evaluate the method allowing to give an optimal spectrum so that the interpretation can be done easily. In addition, and for the purpose of the defects quantification, we have done an optimization on the magnetic powders, colored and fluorescent, by applying magnetic powders of variable dimensions. This will enable us to estimate defects with a high precision. 

The external reflection of infrared radiation can be used to characterize the thickness and orientation of adsorbates on metal surfaces. Buontempo and Rice [153-155] have recently extended this technique to molecules at dielectric surfaces, including Langmuir monolayers at the air-water interface. Analysis of the dichroic ratio, the ratio of reflectivity parallel to the plane of incidence (p-polarization) to that perpendicular to it (.r-polarization) allows evaluation of the molecular orientation in terms of a tilt angle and rotation around the backbone [153]. An example of the p-polarized reflection spectrum for stearyl alcohol is shown in Fig. IV-13. Unfortunately, quantitative analysis of the experimental measurements of the antisymmetric CH2 stretch for heneicosanol [153,155] stearly alcohol [154] and tetracosanoic [156] monolayers is made difflcult by the scatter in the IR peak heights. 

Other methods consist of algorithms based on multivariate classification techniques or neural networks they are constructed for automatic recognition of structural properties from spectral data, or for simulation of spectra from structural properties [83]. Multivariate data analysis for spectrum interpretation is based on the characterization of spectra by a set of spectral features. A spectrum can be considered as a point in a multidimensional space with the coordinates defined by spectral features. Exploratory data analysis and cluster analysis are used to investigate the multidimensional space and to evaluate rules to distinguish structure classes. 

The approach to the evaluation of vibrational spectra described above is based on classical simulations for which quantum corrections are possible. The incorporation of quantum effects directly in simulations of large molecular systems is one of the most challenging areas in theoretical chemistry today. The development of quantum simulation methods is particularly important in the area of molecular spectroscopy for which quantum effects can be important and where the goal is to use simulations to help understand the structural and dynamical origins of changes in spectral lineshapes with environmental variables such as the temperature. The direct evaluation of quantum time- correlation functions for anharmonic systems is extremely difficult. Our initial approach to the evaluation of finite temperature anharmonic effects on vibrational lineshapes is derived from the fact that the moments of the vibrational lineshape spectrum can be expressed as functions of expectation values of positional and momentum operators. These expectation values can be evaluated using extremely efficient quantum Monte-Carlo techniques. The main points are summarized below. 

These results obtained from the analyses of industrial blends proved that the identification of the constituents of the different surfactant blends in the FIA-MS and MS-MS mode can be performed successfully in a time-saving manner only using the product ion scan carried out in mixture analysis mode. The applicability of positive ionisation either using FIA-MS for screening and MS-MS for the identification of these surfactants was evaluated after the blends examined before were mixed resulting in a complex surfactant mixture (cf. Fig. 2.5.7(a)). Identification of selected mixture constituents known to belong to the different blends used for mixture composition was performed by applying the whole spectrum of analytical techniques provided by MS-MS such as product ion, parent ion and/or neutral loss scans. 

Level 1 sampling provides a single set of samples acquired to represent the average composition of each stream. This sample set is separated, either in the field or in the laboratory, into solid, liquid, and gas-phase components. Each fraction is evaluated with survey techniques which define its basic physical, chemical, and biological characteristics. The survey methods selected are compatible with a very broad spectrum of materials and have sufficient sensitivity to ensure a high probability of detecting environmental problems. Analytical techniques and instrumentation have been kept as simple as possible in order to provide an effective level of information at minimum cost. Each individual piece of data developed adds a relevant point to the overall evaluation. Conversely, since the information from a given analysis is limited, all the tests must be performed to provide a valid assessment of the sample. 

In Section II, the deconvolution examples used noise-free simulated spectra. Any real spectrum will be corrupted by noise. The noise can be reduced by smoothing, but smoothing generally attenuates high spectral frequencies in data. There is an operational conflict, however, because it is these same high spectral frequencies that we wish to enhance by deconvolution. In this section, the effects of noise on deconvolution are demonstrated and several smoothing techniques are evaluated. 

---