Raman Microspectroscopy of Old Paper Samples with Foxing

Diagnostic methods and historical document and artwork (in particular, paper items) analysis using modern physical methods is a topical practical problem. Paper materials exhibit nonuniform degradation with the formation of foxing stains. Correct physico-chemical identification of the structure of foxed fragments depends on the efficiency of the experimental technique and offers guidelines for restoration. Raman spectroscopy makes it possible to characterize old paper samples; however, to our knowledge, a comprehensive Raman analysis of foxing has not been done. In this study, we demonstrate that Raman microspectroscopy allows the identification of spectral changes related to paper aging and foxing formation. The degree of degradation of the rag papers studied here is noticeably less than the degree of degradation of the wood-cellulose papers. The spectral differences among 19th-, 20th-, and 21st-century papers are revealed. The presence of lignin and gypsum filler in the 20th-century paper is demonstrated. Raman data indicate that the foxed fragments exhibit a stronger degradation of the paper. The spectral differences between the foxed and unfoxed fragments are discussed. The results can be used in the restoration of paper documents and artworks, in particular for identification of foxed fragments.