Sample analysis techniques

If the solid can be dissolved in a suitable solvent, then the same method as for a liquid is followed although no solvent exists which is transparent across the whole range of the mid-IR. This procedure permits of quantitative measurements to be performed at all wavelength except those absorbed by the solvent. 

Nujol presents three major absorption bands beyond which the spectrum of the sample is exploitable. This spectrum can be supplemented by another carried out in hexachlorobutadiene, transparent in the regions where paraffin absorbs. For the KBr technique, the sample is crushed with KBr in an agate mortar. The mixture is then pressed using an hydraulic press (pressure of 5 to 8t/cm ) or manually into a transparent disc. 

When a light beam impacts at the surface of a medium for which the refractive index is different it can undergo, depending upon the angle of incidence and the variation of the refractive index, either a total reflection as in a mirror, or an attenuated reflection after having in part penetrated into the second medium (just a few micrometres for the mid-IR). The spectral composition of the beam reflected depends of the compound studied and upon the way in which the refractive index of the material varies with the wavelength. 

This accessory, which can only be used with FTIR spectrometers, is a nondestructive method reserved for samples which reflect at least a minimum of 

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Seeley and Skogerboe have described a combined sampling-analysis technique for the determination of trace elements in particulate matter in the atmosphere. Porous cup graphite spectroscopic electrodes are used as filters to collect the particulates and then form the sample electrode for emission spectroscopic determination of element concentrations. 

Isotopic dilution analysis is widely used to determine the amounts of trace elements in a wide range of samples. The technique involves the addition to any sample of a known quantity (a spike) of an isotope of the element to be analyzed. By measuring isotope ratios in the sample before and after addition of the spike, the amount of the trace element can be determined with high accuracy. The method is described more fully in Figure 48.13. 

Microscopy (qv) plays a key role in examining trace evidence owing to the small size of the evidence and a desire to use nondestmctive testing (qv) techniques whenever possible. Polarizing light microscopy (43,44) is a method of choice for crystalline materials. Microscopy and microchemical analysis techniques (45,46) work well on small samples, are relatively nondestmctive, and are fast. Evidence such as sod, minerals, synthetic fibers, explosive debris, foodstuff, cosmetics (qv), and the like, lend themselves to this technique as do comparison microscopy, refractive index, and density comparisons with known specimens. Other microscopic procedures involving infrared, visible, and ultraviolet spectroscopy (qv) also are used to examine many types of trace evidence. 

Like the refining of the PGMs, the analysis is compHcated by the chemical similarity of the metals. The techniques used depend on the elements present and their concentration in the sample. For some low grade samples, analysis is preceded by a concentration stage using fire assay with collection into a lead or nickel sulfide button. The individual metals can then be determined. 

A large number of radiometric techniques have been developed for Pu analysis on tracer, biochemical, and environmental samples (119,120). In general the a-particles of most Pu isotopes are detected by gas-proportional, surface-barrier, or scintillation detectors. When the level of Pu is lower than 10 g/g sample, radiometric techniques must be enhanced by preliminary extraction of the Pu to concentrate the Pu and separate it from other radioisotopes (121,122). Alternatively, fission—fragment track detection can detect Pu at a level of 10 g/g sample or better (123). Chemical concentration of Pu from urine, neutron irradiation in a research reactor, followed by fission track detection, can achieve a sensitivity for Pu of better than 1 mBq/L (4 X 10 g/g sample) (124). 

Statistical control of an analysis or instmment is best demonstrated by SQC of a standard sample analysis. The preferred approach to demonstrate statistical control is to use a reference sample of the subject material that has been carefully analyzed or, alternatively, to use a purchased reference standard. Either material must be stored so that it remains unchanged, eg, sealed in ampuls or septum capped bottles. Periodically a sample can then be reanalyzed by the technique used for routine analysis. These results are plotted in a control chart. Any change in the stabihty of the test in question results in a lack of... 

The field of steroid analysis includes identification of steroids in biological samples, analysis of pharmaceutical formulations, and elucidation of steroid stmctures. Many different analytical methods, such as ultraviolet (uv) spectroscopy, infrared (ir) spectroscopy, nuclear magnetic resonance (nmr) spectroscopy, x-ray crystallography, and mass spectroscopy, are used for steroid analysis. The constant development of these analytical techniques has stimulated the advancement of steroid analysis. 

On-Hne Procedures The growing trend toward automation in industry has resiilted in many studies of rapid procedures for generating size information so that feedback loops can be instituted as an integral part of a process. Many of these techniques are modifications of more traditional methods. The problems associated with on-line methods include allocation and preparation of a representative sample analysis of the sample evaluation of the results. The interface between the measuring apparatus and the process has the potential of high complexity, and consequently, high costs [Leschonsld, Paiticle Cha racterization, 1, 1 (July 1984)]. 

The chemical composition of particulate pollutants is determined in two forms specific elements, or specific compounds or ions. Knowledge of their chemical composition is useful in determining the sources of airborne particles and in understanding the fate of particles in the atmosphere. Elemental analysis yields results in terms of the individual elements present in a sample such as a given quantity of sulfur, S. From elemental analysis techniques we do not obtain direct information about the chemical form of S in a sample such as sulfate (SO/ ) or sulfide. Two nondestructive techniques used for direct elemental analysis of particulate samples are X-ray fluorescence spectroscopy (XRF) and neutron activation analysis (NAA). 

The STEM instrument itself can produce highly focused high-intensity beams down to 2 A if a field-emission source is used. Such an instrument provides a higher spatial resolution compositional analysis than any other widely used technique, but to capitalize on this requires very thin samples, as stated above. EELS and EDS are the two composition techniques usually found on a STEM, but CL, and even AES are sometimes incorporated. In addition simultaneous crystallographic information can be provided by diffraction, as in the TEM, but with 100 times better spatial resolution. The combination of diffraction techniques and analysis techniques in a TEM or STEM is termed Analytical Electron Microscopy, AEM. A well-equipped analytical TEM or STEM costs well over 1,000,000. 

Auger electron spectroscopy is the most frequently used surface, thin-film, or interface compositional analysis technique. This is because of its very versatile combination of attributes. It has surface specificity—a sampling depth that varies... 

A somewhat related technique is that of laser ionization mass spectrometry (LIMS), also known as LIMA and LAMMA, where a single pulsed laser beam ablates material and simultaneously causes some ionization, analogous to samples beyond the outer surface and therefore is more of a bulk analysis technique it also has severe quantiBaction problems, often even more extreme than for SIMS. 

Approximately 70 different elements are routinely determined using ICP-OES. Detection limits are typically in the sub-part-per-billion (sub-ppb) to 0.1 part-per-million (ppm) range. ICP-OES is most commonly used for bulk analysis of liquid samples or solids dissolved in liquids. Special sample introduction techniques, such as spark discharge or laser ablation, allow the analysis of surfaces or thin films. Each element emits a characteristic spectrum in the ultraviolet and visible region. The light intensity at one of the characteristic wavelengths is proportional to the concentration of that element in the sample. 

ICP-OES is one of the most successful multielement analysis techniques for materials characterization. While precision and interference effects are generally best when solutions are analyzed, a number of techniques allow the direct analysis of solids. The strengths of ICP-OES include speed, relatively small interference effects, low detection limits, and applicability to a wide variety of materials. Improvements are expected in sample-introduction techniques, spectrometers that detect simultaneously the entire ultraviolet—visible spectrum with high resolution, and in the development of intelligent instruments to further improve analysis reliability. ICPMS vigorously competes with ICP-OES, particularly when low detection limits are required. 

Initial results prove the high potential of LA-based hyphenated techniques for depth profiling of coatings and multilayer samples. These techniques can be used as complementary methods to other surface-analysis techniques. Probably the most reasonable application of laser ablation for depth profiling would be the range from a few tens of nanometers to a few tens of microns, a range which is difficult to analyze by other techniques, e. g. SIMS, SNMS,TXRE, GD-OES-MS, etc. The lateral and depth resolution of LA can both be improved by use of femtosecond lasers. 

A number of techniques are available for determining the composition of a solid surface. Since the surface plays an important role in many processes, such as oxidation, discoloration, wear, and adhesion, these techniques have gained importance. The choice of a surface analysis technique depends upon such important considerations as sampling depth, surface information, analysis environment, and sample suitability. Different... 

Lubricating oil analysis, as the name implies, is an analysis technique that determines the condition of lubricating oils used in mechanical and electrical equipment. It is not a tool for determining the operating condition of machinery. Some forms of lubricating oil analysis will provide an accurate quantitative breakdown of individual chemical elements, both oil additive and contaminates, contained in the oil. A comparison of the amount of trace metals in successive oil samples can indicate wear patterns of oil wetted parts in plant equipment and will provide an indication of impending machine failure. 

Lubricating oil samples from all equipment included in the program should be taken on a monthly basis. As a minimum, a full spectrographic analysis should be conducted on these samples. Wear particle or other analysis techniques should be made on an as-needed basis. 

Ion chromatography has been successfully applied to the quantitative analysis of ions in many diverse types of industrial and environmental samples. The technique has also been valuable for microelemental analysis, e.g. for the determination of sulphur, chlorine, bromine, phosphorus and iodine as heteroatoms in solid samples. Combustion in a Schoniger oxygen flask (Section 3.31 )is a widely used method of degrading such samples, the products of combustion being absorbed in solution as anionic or cationic forms, and the solution then directly injected into the ion chromatograph. 

The above consequences of isothermal operation may be largely avoided by using the technique of programmed-temperature gas chromatography (PTGC) in which the temperature of the whole column is raised during the sample analysis. 

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