We investigated the actual factor determining the softening effect of a fabric softener. The adsorption area of the softener on model cotton cloths and yarns was identified using bromophenol blue. There was almost no softener at the cross-points of the yarns in the cloth samples or in the inner part of the yarns. The softening performance was better when there was less softener at the cross-points of the yarns than when the yarns were evenly covered by the softener. Thus we conclude that the presence of softener at the cross-points of yarns is not a vital factor in the softening effect. In addition, more softener was found on the outer part of the yarn than the inner part, indicating gradation in the adsorption pattern of the softener. Thus, we propose that more softener is adsorbed on the exposed part of the yarn in a cloth, and the formation of a hydrogen-bonding network containing bound water is inhibited, thus softening the outer part of the yarn. However, the presence of a small amount of softener in the inner part of the yarn preserves the hydrogen-bonding network. Favorable elasticity, or bounce, of the yarns and cloth is realized when an appropriate amount of softener is used. Excess softener would reach the inner part of the yarn, reducing the diameter of the core part of the yarn, making the cloth appear wilted.
Broadband dielectric spectroscopy measurements were performed on naturally dried cotton cloth, and a recently developed analytical technique for fractal analysis of water structures was applied to obtain existential states and locations of water molecules in the material. Three relaxation processes observed in GHz, MHz, and kHz frequency regions were attributed to dynamic behaviors of hydrogen bonding networks (HBNs) of water and interacting molecules, polymer chains with interacting ion and water molecules, and ions restricted on the interfaces of larger structures, respectively. Water molecules were heterogeneously distributed in the cotton cloth, and the HBNs remained as a broad GHz frequency process. Fractal analysis suggested that water molecules distributed in the material were characterized by a small value (0.55) of the Cole–Cole relaxation time distribution parameter, indicating spatial distribution of HBN fragments with various sizes in cotton cloth. This result was also supported by the T2 relaxation time obtained from nuclear magnetic resonance for naturally dried cotton yarn. Comparing previous results of dielectric relaxation measurements and fractal analysis with the τ–β diagram for various aqueous systems, the results determined that water molecules cannot exist inside cellulose microfibrils. The fractal analysis employed in this work can be applied to dynamic water structures in any material. The presented analytical technique with a universal τ–β diagram is expected to be an effective tool to clarify water structure detail even for heterogeneous hydrations of the low water content substances.
Graphical abstract
A wet cotton rag becomes stiff after natural drying. We propose a model for this hardening phenomenon, which explains that the stiffness of cotton is caused by a cross-linked network between single fibers, mediated by capillary adhesion of bound water on the surface of cellulose. Here, with the aid of atomic force microscopy and atomic force microscopy−infrared spectroscopy, we reveal the existence of the bound water on the surface of a cotton single fiber under naturally dried conditions. We also find that the hydrogen bonding state of the bound water is distinct from that of the bulk water. Two stretching modes of OH groups are clearly decoupled from each other, which arise from the effects of the air−water (hydrophobic) and water−cellulose (hydrophilic) interfaces. This suggests a possible link between the microscopic nature of the bound water and the macroscopic mechanical behavior of cotton fabrics.
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