Use of Raman spectroscopy and chemometrics to distinguish blue ballpoint pen inks

• Raman spectroscopy and chemometrics were combined to differentiate 14 pen inks.
• Spectral preprocessing removed the fluorescence contribution to Raman signal.
• All inks were successfully differentiated by exploration and classification tools.
• The relevant spectroscopic ranges to differentiate among inks were determined.
• We report a fast, non-destructive and statistically sound method for ink analysis.

The objective of this work is assessing whether the combination of Raman spectroscopy and chemometric tools is appropriate to differentiate blue ballpoint pen inks. Fourteen commercial blue ballpoint pen inks from different brands and models were studied and Raman spectra were obtained on ink lines written on A4 sulfite paper. First, a study of the best Raman configurations, in terms of laser intensity used and acquisition mode, was carried out to ensure sufficient spectroscopic quality without damaging the sample. Chemometric methods were applied first to improve the definition of spectral bands and to suppress fluorescence contributions from the signal. Once the spectra were suitably preprocessed, principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to explore whether the different inks could be distinguished from their Raman spectra. Almost all inks could be gradually differentiated, through successive PCA analyses or looking at the different levels of the dendrogram structure provided by HCA. From these exploratory results, a tree structure was constructed based on PCA and HCA results in order to reflect the degree of similarity among ink classes. This tree structure was used as the basis to develop hierarchical classification models based on partial least squares-discriminant analysis (PLS-DA). Correct classification of inks was achieved by these PLS-DA models built and the most important regions to identify the ink classes were detected using the variable importance in projection plots (VIPs). The combination of Raman spectroscopy and chemometrics has been proven to be a promising fast non-destructive tool to differentiate among very similar ink types in documents.