In situ identification and analysis of automotive paint pigments using line segment excitation Raman spectroscopy: I. Inorganic topcoat pigments

Several applications of Raman spectroscopy in the forensic sciences have recently been demonstrated, but few have involved the analysis of paints. Undoubtedly, this is a reflection of the sample degradation problems often encountered when a visible or near-infrared laser is focused on a light-absorbing matrix. In this study, a dispersive CCD Raman spectrometer (785 nm) was used in a configuration which collected scattered light from an excitation region 3 mm long and 80 microm wide, instead of from a focused spot. Sample degradation was not observed, and Raman spectra of automotive paints of all colors were readily obtained. Most of the paints analyzed were U.S. automobile original finishes (1974 to 1989) from the Reference Collection of Automotive Paints, and the inorganic pigments examined were those which had been identified previously by infrared spectroscopy in finishes from this collection. Prominent peaks of rutile were observed in Raman spectra of light-colored nonmetallic finishes for both monocoats and basecoat/clearcoat systems, and the rutile peaks are readily distinguished from those of anatase. The lead chromates (Chrome Yellow, Molybdate Orange, and silica-encapsulated versions of the two) are the strongest Raman scatterers among the pigments examined, and Chrome Yellow was identified by Raman spectroscopy in several yellow and orange nonmetallic monocoats for which infrared absorptions of this pigment were not observed. Raman spectroscopy also provides an unequivocal means to distinguish Chrome Yellow from Molybdate Orange. This is particularly helpful for the analysis of paints containing light pigment loads or encapsulated pigments since the two formulations cannot be differentiated by infrared spectroscopy in such cases. The iron-containing pigments, ferric oxide, hydrous ferric oxide, and Prussian Blue, are relatively weak Raman scatterers, but peaks of hydrous ferric oxide and Prussian Blue were observed in spectra of paints containing heavy pigment loads. Because no sample preparation is required. Raman spectroscopy provides an excellent means to rapidly screen reference panels for the presence of certain pigments, and some examples of the differences in Raman spectra which occur for paints having similar colors are presented.     

The coalition of the willing: Effect of country diversity in an environmental treaty game

It is analyzed how size differences among countries affect the benefits from climate coalitions. It is shown that size differences lead to smaller coalitions and greater benefits than coalitions among identical countries. The importance of trigger strategies for supporting cooperative solutions is considered. A real world example, based on the world’s six largest emitters, is used to illustrate the implications of size differences in terms of emissions versus valuations of benefits. Climate coalitions become smaller when ranking in terms of benefits is different from ranking in terms of emissions. Three cases of benefit valuations are considered: benefits equal (i) share in world emissions, (ii) share in world GDP, and (iii) share of world population.