Quantitative analysis amorphous materials

The use of Equation (22) is very general, but it is also possible, with accurate measurements and data treatment, to perform the quantitative phase analysis in semi-crystalline materials without using any internal standard. This procedure is possible only if the chemical compositions of all the phases, including the amorphous one, are known. If the composition of the amorphous phase is unknown, the quantitative analysis without using any internal standard can still be used provided that the chemical composition of the whole sample is available [51]. This approach, until now, has been developed only for the XRD with Bragg-Brentano geometry that is one of the most diffused techniques in powder diffraction laboratories. 

The evolution in calorimetry technology has also led to the development of protocols for quantitative analysis (Buckton and Darcy 1999). Fiebich and Mutz (1999) determined the amorphous content of desferal using both isothermal microcalorimetry and water vapour sorption gravimetry with a level of detection of less than 1 per cent amorphous material. The heat capacity jump associated with the glass transition of amorphous materials MTDSC was used to quantify the amorphous content of a micronised drag substance with a limit of detection of 3 per cent w/w of amorphous... 

While all pyrolysis oil production reactor systems produce similar materials, each reactor produces a unique compound slate. The first decision, especially for a potential chemical or fuel producer, rather than a reactor developer, is to determine what products to make and which reactor system to use. The operating parameters of any reactor system designed to produce pyrolysis oil, especially temperature, can be altered to change the pyrolysis oil product composition and yield. Different feedstocks will produce different pyrolysis oil compositions and by-products, e.g. amorphous silica from rice hulls or rice straw, fatty acids from pine. Finally, feedstock pretreatment and/or catalysis, or reactor-bed catalysis can be used to improve specific product yields (7). Reactor system developers need to examine what they can produce and make this information available to chemical manufacturers and suppliers/owners of biomass feedstocks. This assumes that analysis of die entire liquid product from thermal conversion can be made, including quantitative analysis for any compounds that are being considered for recoveiy. Physical characterization - pH, viscosity, solids content, etc.is also needed. However, what can be produced is of no value, if it cannot be recovered or used economically. This involves examining the trade-offs between yield and current commercial value, recovery costs, and potential commercial value,... 

In polymer characterization, it is possible to determine the degree of crystallinity of semicrystalline polymers. The noncrystalline (amorphous) portion simply scatters the X-ray beam to give a continuous background, whereas the crystalline portion gives diffraction lines. A typical schematic diffraction spectrum of a semicrystalline polymer is shown in Fig. 8.46. The ratio of the area of diffraction peaks to scattered radiation is proportional to the ratio of crystalline to noncrystalline material in the polymer. The ultimate quantitative analysis must be confirmed using standard polymers with known percent crystallinity and basing the calculation on the known ratio of crystalline diffraction to amorphous scattering. 

In the characterization of building and construction materials, the most frequently analytical tool performed have been X-ray diffraction but also, thermal analysis and microscopic techniques. Nowadays, infrared and other spectroscopic techniques have become as a useful, non-destructive and easy technique to study the phase composition of initial but also the evolved materials due to their exposure to the climatic conditions. Moreover, by using this tool is possible the detection of crystalline but also the amorphous phases very frequently developed on certain cementitious materials, mainly at early ages. The infrared spectroscopy is used both to gather information about the structure of compoimds and as analytical tool to assess in qualitative and quantitative analysis of mixtures. 

Choosing a representative standard is an important part of quantitative analysis. Although there are numerous factors that induce variability in standard data, the most important are composition and order/ disorder variations. It is obviously very important to be certain that standards contain 100% crystalline material and no amorphous material. 

A second problem in the use of DSC for quantitative analysis is that as the degree crystallinity falls so does the heat of fusion. This results in a decreasing sensitivity of DSC for species of lower crystallinity. At its limit DSC does not detect amorphous material. In TREF on the other hand, the detector is sensitive to the hydrocarbon nature of the polymer chain and is not influenced by the crystallinity of the component molecule because detection takes place in solution. The result is that the relative amount of a polyolefin component in a blend can be directly estimated from the peak area without prior calibration. 

The reporting of mica in soil clays depends somewhat on the method of detection. Jackson and Mackenzie [1964] state that some soil clays, which show no indication of mica based on X-ray diffraction, may contain from 5 to 20 % or more of micas based on chemical analysis and on the basis of 10% K2O in mica. According to Schuffelen and van der Marel [1955], soils high in allophane fix very considerable quantitities of potassium. Thus, potassium does not necessarily reside altogether in micas and feldspars in soils. Some of it may be in amorphous material. However, some of the potassium may be in micalike zones of particles, which are largely montmorillonite or vermiculite and have weathered from micas. Such zones may be too small to be detected by X-ray diffraction (Knibbe and Thomas [1972]). 

Solid state NMR is a relatively recent spectroscopic technique that can be used to uniquely identify and quantitate crystalline phases in bulk materials and at surfaces and interfaces. While NMR resembles X-ray diffraction in this capacity, it has the additional advantage of being element-selective and inherently quantitative. Since the signal observed is a direct reflection of the local environment of the element under smdy, NMR can also provide structural insights on a molecularlevel. Thus, information about coordination numbers, local symmetry, and internuclear bond distances is readily available. This feature is particularly usefrd in the structural analysis of highly disordered, amorphous, and compositionally complex systems, where diffraction techniques and other spectroscopies (IR, Raman, EXAFS) often fail. 

This approach is an alternative to quantitative metallography and in the hands of a master gives even more accurate results than the rival method. A more recent development (Chen and Spaepen 1991) is the analysis of the isothermal curve when a material which may be properly amorphous or else nanocrystalline (e.g., a bismuth film vapour-deposited at low temperature) is annealed. The form of the isotherm allows one to distinguish nucleation and growth of a crystalline phase, from the growth of a preexisting nanocrystalline structure. 

With a Fourier transformation of (k) in the distance space, one obtains a separation of the contribution of the various coordination shells. This Fourier transform yields the structural parameters Rj, Nj and ah and thus the near range order of the specimen with respect to the absorbing atoms. The EXAFS analysis for the different absorber atoms within the material yields their specific near range order. Thus, one may get the structure seen form several kinds of absorbing atoms. EXAFS does not require highly crystalline materials. It is a suitable method to study disordered, or even amorphous, structures. The a values provide quantitative information about the thermal and structural disorder. 

An accurate quantitative determination of the sp content with respect to sp2 is not possible by Raman spectroscopy [39], since the actual Raman cross section of linear chains and rings embedded in the carbon amorphous network is not known. Nevertheless, the integrated intensity of the carbyne peak is directly related to the carbyne amount in the network and was thus chosen as the main parameter relating to their evolution. Owing to the amorphous character of the material, gaussian fitting functions have been chosen for the analysis of Raman peaks. 

---