Molecular changes during tensile deformation of single wood fibers followed by Raman microscopy.

Raman spectra were acquired in situ during tensile straining of mechanically isolated fibers of spruce latewood. Stress-strain curves were evaluated along with band positions and intensities to monitor molecular changes due to deformation. Strong correlations (r = 0.99) were found between the shift of the band at 1097 cm(-1) corresponding to the stretching of the cellulose ring structure and the applied stress and strain. High overall shifts (-6.5 cm(-1)) and shift rates (-6.1 cm(-1)/GPa) were observed. After the fiber failed, the band was found on its original position again, proving the elastic nature of the deformation. Additionally, a decrease in the band height ratio of the 1127 and 1097 cm(-1) bands was observed to go hand in hand with the straining of the fiber. This is assumed to reflect a widening of the torsion angle of the glycosidic C-O-C bonding. Thus, the 1097 cm(-1) band shift and the band height ratio enable one to follow the stretching of the cellulose at a molecular level, while the lignin bands are shown to be unaffected. Observed changes in the OH region are shown and interpreted as a weakening of the hydrogen-bonding network during straining. Future experiments on different native wood fibers with variable chemical composition and cellulose orientation and on chemically and enzymatically modified fibers will help to deepen the micromechanical understanding of plant cell walls and the associated macromolecules.