The efficacy and potential of Raman spectroscopy in characterization of a commercial Ordinary Portland Cement (OPC) and three fly ashes (FA's), and their evolving hydration products were studied in this Master's thesis work. While there have been several studies focusing on the application of Raman spectroscopy to synthetic, pure samples, work on commercial cementitious systems is scarce. This work covers this gap by evaluating mixtures containing cements and fly ashes.

The study first involved determination followed by establishment of instrumental configuration and testing parameters optimum for studying cementitious materials both in the dry and wet form. It was found that by tweaking several parameters, collection methodologies and analysis techniques, improved, representative and reproducible data could be obtained. Mapping a representative area to determine the spatial distribution and concentration of sulfates and hydroxides on sample surfaces was found to be the most effective way to study these complex and heterogeneous systems.

The Raman dry analysis of OPC and three different FA's of varying calcium contents and reactivity was able to identify the major mineralogical phases in these binders and the results were in correlation with the X-ray diffraction data. The observed calcium and sulfate phases and their relative concentration also agreed well with the supplementary compositional data obtained from X-ray fluorescence and Atomic absorption spectrometry.

The wet analysis of pastes prepared with 100% OPC and 50%OPC+50%FA(1,2,3) followed the hydration process of the systems for 56 days (0, 0.2, 2, 4, 8, 12, 16, 20, 24, 48, 72 hours, 7, 14, 21, 28, and 56 days). Consistency of trends in the hydration mechanism of such pastes was only obtained when studies were focused on narrow wavenumber ranges: 950-1050 cm-1 for evolution of sulfates and 3600-3700cm-1 for evolution of hydroxides. Gradual disappearance of Gypsum with a parallel formation of Ettringite was clearly visible in most mixes, while transition of AFt to AFm was not very obvious and needs further research. Evolution of hydroxides showed the gradual spatial growth of portlandite in the studied areas of the samples. The growth rate and concentration of portlandite in different fly ash-cement-water mixes was correlated to the reactivity of the given fly ashes. While a clear connection wasnot established, several observations were made based on the interpretation of the obtained data. This lack of agreement between expected and observed results may be attributed to the heterogeneity of the studied materials, potential problems in sample preparations as well as limitations of the technique.

Overall, Raman was effectively applied to the study of commercial, cementitious systems - this work being one of the early attempts if not the first attempt to study multi-phase fly ash blended cement pastes. While Raman may not be able to completely characterize and analyze such systems as a standalone tool, it definitely has a great potential in serving as a supplementary tool for deeper understanding of cement chemistry and hydration mechanisms.