This contribution focuses on understanding of paper wet-strength properties, by taking a closer look at the spatial distribution of wet-strengthening polymers inside the cellulosic fiber network deposited under different treatment conditions using confocal laser scanning microscopy as in situ imaging tool. We compare the behavior of paper samples treated with a photochemically cross-linkable copolymer using an impregnation process employing three different solvents, namely water, 2-propanol (IPA) and 1-butanol (BuOH), respectively. As these solvents swell paper fibers to quite different extents, the deposition of the polymer, on, in or in-between the cellulosic fibers varies quite strongly, as is shown by in-depth analysis using confocal laser scanning microscopy. The difference in accessibility of distinct surface sites exclusively on or also in and between the fibers controls the macroscopic tensile strength under both dry and wet conditions.

An efficient approach employing 4-dimethylaminopyridine and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride as the coupling reagent is presented, which enables the functionalization of cotton linter paper substrates with the 19 F spin label N-boc-cis-4-fluoro-L-proline. This spin label can be easily quantified by 19 F magic angle spinning (MAS) NMR experiments to determine its loading on paper substrates. During the functionalization, the spin label stays intact, as confirmed by the 1 H− 19 F heterocorrelation ( 1 H → 19 F CP MAS FSLG HETCOR) experiments. In combination with dynamic nuclear polarization ( 19 F MAS DNP), the N-boc-cis-4-fluoro-L-proline spin label allows us to inspect 1 μmol/g and even lower molecule loadings on paper substrates, providing a highly sensitive local probe to analyze the structure of biofunctionalizations at the nanoscale on paper substrates in the future.

We present an alternative to commonly used, but from an environmental point of view, problematic wet strength agents, which are usually added to paper to prevent a loss of mechanical stability and finally disintegrate when they get into contact with water. To this end, diazoester-containing copolymers are generated, which are coated onto paper and by heating to 110–160 °C for short periods of time become activated and form carbene intermediates, which undergo a CH-insertion cross-linking reaction. The process leads to a simultaneous cross-linking of the polymer and its attachment to the cellulose substrate. The immobilization process of copolymers consisting of a hydrophilic matrix based on N,N-dimethylacrylamide and a diazoester-based comonomer to a cellulose model surface and to laboratory-engineered, fibrous paper substrates is investigated as a function of time, temperature, and cross-linker composition. The distribution of the polymer in the fiber network is studied using confocal fluorescence microscopy. Finally, the tensile properties of modified wet and dry eucalyptus sulfate papers are measured to demonstrate the strong effect of the thermally cross-linked copolymers on the wet strength of paper substrates. Initial experiments show that the tensile indices of the modified and wetted paper samples are up to 50 times higher compared to the values measured for unmodified samples. When dry and wet papers coated with the above-described wetting agents are compared, relative wet strengths of over 30% are observed.

Functional coatings for application on surfaces are of growing interest. Especially in the textile industry, durable water and oil repellent finishes are of special demand for implementation in the outdoor sector, but also as safety-protection clothes against oil or chemicals. Such oil and chemical repellent textiles can be achieved by coating surfaces with fluoropolymers. As many concerns exist regarding (per)fluorinated polymers due to their high persistence and accumulation capacity in the environment, a durable and resistant coating is essential also during the washing processes of textiles. Within the present study, different strategies are examined for a durable resistant cross-linking of a novel fluoropolymer on the surface of fibers. The monomer 2-((1,1,2-trifluoro-2-(perfluoropropoxy)ethyl)thio)ethyl acrylate, whose fluorinated side-chain is degradable by treatment with ozone, was used for this purpose. The polymers were synthesized via free radical polymerization in emulsion, and different amounts of cross-linking reagents were copolymerized. The final polymer dispersions were applied to cellulose fibers and the cross-linking was induced thermally or by irradiation with UV-light. In order to investigate the cross-linking efficiency, tensile elongation studies were carried out. In addition, multiple washing processes of the fibers was performed and the polymer loss during washing, as well as the effects on oil and water repellency were investigated. The cross-linking strategy paves the way to a durable fluoropolymer-based functional coating and the polymers are expected to provide a promising and sustainable alternative to functional coatings.

Paper materials are well-known to be hydrophilic unless chemical and mechanical processing treatments are undertaken. The relative humidity impacts the fiber elasticity, the interfiber joint behavior and the failure mechanism. In this work, we present a comprehensive experimental and computational study on mechanical properties of the fiber and the fiber network under humidity influence. The manually extracted cellulose fiber is exposed to different levels of humidity, and then mechanically characterized using atomic force microscopy, which delivers the humidity dependent longitudinal Young’s modulus. We describe the relation and calibrate the data into an exponential function, and the obtained relationship allows calculation of fiber elastic modulus at any humidity level. Moreover, by using confoncal laser scanning microscopy, the coefficient of hygroscopic expansion of the fibers is determined. We further present a finite element model to simulate the deformation and the failure of the fiber network. The model includes the fiber anisotropy and the hygroscopic expansion using the experimentally determined constants, and further considers interfiber behavior and debonding by using a humidity dependent cohesive zone interface model. Simulations on exemplary fiber network samples are performed to demonstrate the influence of different aspects including relative humidity and fiber-fiber bonding parameters on the mechanical features, such as force-elongation curve, strength and extensibility. Finally, we provide computational insights for interfiber bond damage pattern with respect to different humidity level as further outlook.