Surface hydrophobicity modification of cellulose fibers by layer-by-layer self-assembly of lignosulfonates

Self-assembled multilayers of lignosulfonates (LS) were built up on both quartz slides and cellulose fibers using a Cu2+-mediated layer-by-layer (LBL) technique. The growth of LS multilayers on quartz slides was monitored by UV-Vis spectroscopy, and the absorbance at 205 nm as well as at 280 nm was found to linearly increase with the number of layers. The formation of LS multilayers on fibers surfaces was characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The XPS results showed that the surface contents of the characteristic elements, S and Cu, of LS multilayers were increased with the number of layers, which suggests the deposition of LS-Cu2+ complexes on cellulose fibers. Furthermore, there was a good linear relationship between the calculated surface LS content and the increment of LS layers. The AFM morphology results confirmed that the cellulose microfibrils on fiber surface were gradually covered by LS particles, resulting in the increase of surface roughness as self-assembly proceeded. The hydrophobicity of cellulose fiber probed by dynamic contact angle was significantly increased due to LBL self-assembly of LS on its surface. The initial contact angle was increased from 0° to 115° as the cellulose fibers were modified with a 5-layer LS multilayer. The reduction rate of the contact angle was dependent on the number of layers. When the cellulose fiber was modified by a 5-layer LS multilayer, the contact angle shifted from 115 to 98° after 0.12 s, suggesting some degree of hydrophobic character. Therefore, this technique provides a simple but effective way for promoting hydrophobicity of cellulose fibers in a controllable manner.