Analysis of Solids

Solids can be measured in transmission or reflection (reflectance) modes. Both specular reflection and diffuse reflection are used. Diffuse reflection accessories include the Praying Mantis from Harrick Scientific Products, Inc., and a variety of integrating spheres available from most major instrument companies. Specular reflection is used for highly reflective materials diffuse reflectance for powders and rough surfaced solids. Materials characterization relies heavily on techniques like these. 

The Praying Mantis and its high-temperature reaction chamber have been used for studying temperature-induced wavelength changes in Thermal Liquid Crystal Paint, analyzing gas-soUd reactions such as heterogeneous catalysis, and routine analysis of powders and solids. Application notes can be found at www.harricksci.com. 

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For solids, there is now a very wide range of inlet and ionization opportunities, so most types of solids can be examined, either neat or in solution. However, the inlet/ionization methods are often not simply interchangeable, even if they use the same mass analyzer. Thus a direct-insertion probe will normally be used with El or Cl (and desorption chemical ionization, DCl) methods of ionization. An LC is used with ES or APCI for solutions, and nebulizers can be used with plasma torches for other solutions. MALDI or laser ablation are used for direct analysis of solids. 

The control of processes involving the treatment of solids generally requires means for careful samphng and analysis of solids and slurries at various points in an operation. Unlike liquids, particulate solids are not homogeneous. The composition of individual particles will vaiy with particle size and particle density. It follows that care must be... 

Laser based mass spectrometric methods, such as laser ionization (LIMS) and laser ablation in combination with inductively coupled plasma mass spectrometry (LA-ICP-MS) are powerful analytical techniques for survey analysis of solid substances. To realize the analytical performances methods for the direct trace analysis of synthetic and natural crystals modification of a traditional analytical technique was necessary and suitable standard reference materials (SRM) were required. Recent developments allowed extending the range of analytical applications of LIMS and LA-ICP-MS will be presented and discussed. For example ... 

For quantitative analysis of solid supported thiol residues on free macroporous or PEG grafts, Ellman s reagent has been used [5,5 -dithio-hfr-(2-nitrobenzoic acid]. However only qualitative information can be gained using lightly crosslinked polystyrene resins [Badyal et al. Tetrahedron Lett 42 8531 2007]. 

Atomic structure and Microstructural analysis of solid materials, providing high lateral resolution... 

Major applications of CL microscopy and spectroscopy in the analysis of solids have been listed in the Introduction. Some specific examples of CL applications are outlined below. 

Since the 1950s XRF has been used extensively for the analysis of solids, powders, and liquids. The technique was extended to analyze thin-film materials in the 1970s. XRF can be used routinely for the simultaneous determination of elemental composition and thickness of thin films. The technique is nondesuuctive, rapid, precise, and potentially very accurate. The results are in good agreement with other elemental analysis techniques including wet chemical, electron-beam excitation techniques, etc. 

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. 

The most common ions observed as a result of electron-stimulated desorption are atomic (e. g., H, 0, E ), but molecular ions such as OH", CO", H20, and 02" can also be found in significant quantities after adsorption of H2O, CO, CO2, etc. Substrate metallic ions have never been observed, which means that ESD is not applicable to surface compositional analysis of solid materials. The most important application of ESD in the angularly resolved form ESDIAD is in determining the structure and mode of adsorption of adsorbed species. This is because the ejection of positive ions in ESD is not isotropic. Instead the ions are desorbed along specific directions only, characterized by the orientation of the molecular bonds that are broken by electron excitation. 

As already remarked in Sect. 4.5.1 (Introduction), LA was primarily designed as a technique for direct sampling in the bulk analysis of solid samples. The main advantages of LA are the possibility of ablating all types of solid material (metals, isolators, glasses, crystals, minerals ceramics, etc.), no special requirements on the... 

Ail the parameters on which various consents (or permissions to dispose of, waste streams) are based must be reliably measured and recorded. This is easier to achieve with gaseous emissions (Chapter 10) and liquid effluents than with heterogeneous solid wastes. Systematic analysis of solid wastes will cover as a minimum the information in Table 17.15. 

Ahearn, Mass Spectrometric Analysis of Solids, Elsevier, NY (1966) 23) M.S.B. Munson ... 

The several distinct derivations of eqn. (6) originally provided [30] by Avrami [436], by Erofe ev [437,448] and by Mampel [447] and developed by others, is a consequence of the importance to be attached to this expression for the kinetic analysis of solid phase reactions. Written in general form... 

Wilson, K. C. Hydrotransporl 4 (BHRA Fluid Engineering, Banff. Alberta, Canada) (May 1976) ALL A unified physically-based analysis of solid-liquid pipeline flow. 

W. Gopel, and H.-D. Wiemhofer, Electrode kinetics and interface analysis of solid electrolytes for fuel cells and sensors, Ber. Buns. Phys. Chem. 94, 981-987 (1990). 

Olund SD, DeWild JF, Olson ML, Tate MT. 2004. Methods for the preparation and analysis of solids and suspended solids for total mercury, U.S. Geological Survey Techniques and Methods Report 5A-8, 23 p. 

Nowka R, Muller H (1997) Direct analysis of solid samples by graphite furnace atomic absorption spectrometry with a transversely heated graphite atomizer and D2-background correction system (SS GF-AAS). Fresenius J Anal Chem 359 132-137. 

Hoffmann E, Ludke C, Scholze H (1997) Is laser ablation-lCP-MS an alternative to solution analysis of solid samples Fresenius J Anal Chem 359 394-398. 

Noweoy R, Marr IL, Ansari TM, Muller H 1999) Direct analysis of solid samples by GFAAS -determination of trace hea-vy metals in barytes. Fresenius ( Anal Chem 364 533-540. 

Verrept P, Dams R, Kurfurst U 1993) Electrothermal vaporisation inductively coupled plasma atomic emission spectrometry for the analysis of solid samples contribution to instrumentation and methodology. Fresenius 2 Anal Chem 345 1035-1041. 

Structural analysis of solids under extreme pressure and temperature conditions... 

SFE has been used extensively in the analysis of solid polymers. Supercritical fluid extraction of liquid samples is undertaken less widely because dissolution or entrainment of the matrix can occur. As illustrated elsewhere SFE has also been applied for the analysis of liquid poly(alkylene glycol) (PAG) lubricants and sorbitan ester formulations [370]. The analysis of PAG additives (antioxidants, biocides and anticorrosion, antiwear and antifoaming agents) is hindered by the presence of the low molecular weight PAG matrix (liquid) and therefore a method for the selective separation of additives from PAG is required. The PAG... 

Analysis of solid matter, in particular of rubber vulcanisates, is a classical application of DP-MS [263]. 

Applications Spark-source atomic emission and mass spectrometry have been used for routine analysis of solids, particularly for quality assurance and comparative work. As with GD-MS, spark sources are restricted to samples that are, to some extent, electrically conducting, or that can be made conducting by... 

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