Luminescence reveals variations in local structural order of calcium carbonate polymorphs formed by different mechanisms.

In nature, calcium carbonate (CaCO3) in the form of calcite and aragonite nucleates through different pathways including geogenic and biogenic processes. It may also occur as pyrogenic lime plaster and laboratory-precipitated crystals. All of these formation processes are conducive to different degrees of local structural order in CaCO3 crystals, with the pyrogenic and precipitated forms being the least ordered. These variations affect the manner in which crystals interact with electromagnetic radiation, and thus formation processes may be tracked using methods such as X-ray diffraction and infrared spectroscopy. Here we show that defects in the crystal structure of CaCO3 may be detected by looking at the luminescence of crystals. Using cathodoluminescence by scanning electron microscopy (SEM-CL) and laser-induced fluorescence (LIF), it is possible to discern different polymorphs and their mechanism of formation. We were thus able to determine that pyrogenic calcite and aragonite exhibit blue luminescence due to the incorporation of distortions in the crystal lattice caused by heat and rapid precipitation, in agreement with infrared spectroscopy assessments of local structural order. These results provide the first detailed reference database of SEM-CL and LIF spectra of CaCO3 standards, and find application in the characterization of optical, archaeological and construction materials.

Characterization and Discrimination of Plastic Materials Using Laser-Induced Fluorescence.

The most meaningful spectral components in laser-induced fluorescence (LIF) spectra for several different commercial plastics have been individuated and used to automatically discriminate among different plastic materials and between plastics and complex organic materials, such as woods. Starting from LIF measurements on known samples, a number of significant wavelengths have been identified by principal component analysis (PCA). These have been used to produce intensity ratios functional to the discrimination. Threshold values for such ratios have been individuated in order to obtain an automatic recognition of plastics. The work done has been preparatory to the design and development of a multispectral imaging LIF system for fast detection of plastic debris in a post-blast scene.