Influence of Surface Charge Density and Morphology on the Formation of Polyelectrolyte Multilayers on Smooth Charged Cellulose Surfaces

To clarify the importance of the surface charge for the formation of polyelectrolyte multilayers, layer-by-layer (LbL) assemblies of polydiallyldimethylammonium chloride (pDADMAC) and polystyrenesulfonate (PSS) have been investigated on cellulose films with different carboxylic acid contents (20, 350, 870, and 1200 μmol/g) regenerated from oxidized cellulose. The wet cellulose films were thoroughly characterized prior to multilayer deposition using quantitative nanomechanical mapping (QNM), which showed that the mechanical properties were greatly affected by the degree of oxidation of the cellulose. Atomic force microscopy (AFM) force measurements were used to determine the surface potential of the cellulose films by fitting the force data to the DLVO theory. With the exception of the 1200 μmol/g film, the force measurements showed a second-order polynomial increase in surface potential with increasing degree of oxidation. The low surface potential for the 1200 μmol/g film was attributed to the low degree of regeneration of the cellulose film in aqueous media due to increasing solubility with increasing charge. The multilayer formation was characterized using a quartz crystal microbalance with dissipation (QCM-D) and stagnation-point adsorption reflectometry (SPAR). Extensive deswelling was observed for the charged films when pDADMAC was adsorbed due to the reduced osmotic pressure when ions inside the film were released, and the 1:1 charge compensation showed that all the charges in the films were reached by the pDADMAC. The multilayer formation was not significantly affected by the charge density above 350 μmol/g due to interlayer repulsions, but it was strongly affected by the salt concentration during the layer build-up

Tailoring Soft Polymer Networks Based on Sugars and Fatty Acids toward Pressure Sensitive Adhesive Applications

The present work describes the synthesis and characterization of fully biobased soft polymer networks for pressure sensitive adhesives applications. The incorporation of different sugars into fatty-acid-based monomers, made it possible to tailor the viscoelastic properties of the materials. Lipase catalysis allowed to afford monomers with varying hydroxyl content and epoxy-functionalities. Step-growth polymerization catalyzed by DBU resulted in soft-polyester networks through combination of the monomers with a biobased diacid. Rheological and adhesion studies were performed to elucidate the different viscoelastic and adhesive properties of the materials as a function of their composition

Direct Adhesive Measurements between Wood Biopolymer Model Surfaces

For the first time the dry adhesion was measured for an all-wood biopolymer system using Johnson–Kendall–Roberts (JKR) contact mechanics. The polydimethylsiloxane hemisphere was successfully surface-modified with a Cellulose I model surface using layer-by-layer assembly of nanofibrillated cellulose and polyethyleneimine. Flat surfaces of cellulose were equally prepared on silicon dioxide substrates, and model surfaces of glucomannan and lignin were prepared on silicon dioxide using spin-coating. The measured work of adhesion on loading and the adhesion hysteresis was found to be very similar between cellulose and all three wood polymers, suggesting that the interaction between these biopolymers do not differ greatly. Surface energy calculations from contact angle measurements indicated similar dispersive surface energy components for the model surfaces. The dispersive component was dominating the surface energy for all surfaces. The JKR work of adhesion was lower than that calculated from contact angle measurements, which partially can be ascribed to surface roughness of the model surfaces and overestimation of the surface energies from contact angle determinations

Adhesive Layer-by-Layer Films of Carboxymethylated Cellulose Nanofibril–Dopamine Covalent Bioconjugates Inspired by Marine Mussel Threads

The preparation of multifunctional films and coatings from sustainable, low-cost raw materials has attracted considerable interest during the past decade. In this respect, cellulose-based products possess great promise due not only to the availability of large amounts of cellulose in nature but also to the new classes of nanosized and well-characterized building blocks of cellulose being prepared from trees or annual plants. However, to fully utilize the inherent properties of these nanomaterials, facile and also sustainable preparation routes are needed. In this work, bioinspired hybrid conjugates of carboxymethylated cellulose nanofibrils (CNFC) and dopamine (DOPA) have been prepared and layer-by-layer (LbL) films of these modified nanofibrils have been built up in combination with a branched polyelectrolyte, polyethyleneimine (PEI), to obtain robust, adhesive, and wet-stable nanocoatings on solid surfaces. It is shown that the chemical functionalization of CNFCs with DOPA molecules alters their conventional properties both in liquid dispersion and at the interface and also influences the LbL film formation by reducing the electrostatic interaction. Although the CNFC–DOPA conjugates show a lower colloidal stability in aqueous dispersions due to charge suppression, it was possible to prepare the LbL films through the consecutive deposition of the building blocks. Adhesive forces between multilayer films prepared using chemically functionalized CNFCs and a silica probe are much stronger in the presence of Fe³⁺ than those between a multilayer film prepared from unmodified nanofibrils and a silica probe. The present work demonstrates a facile way to prepare chemically functionalized cellulose nanofibrils whereby more extended applications can produce novel cellulose-based materials with different functionalities

Water Drop Friction on Superhydrophobic Surfaces

To investigate water drop friction on superhydrophobic surfaces, the motion of water drops on three different superhydrophobic surfaces has been studied by allowing drops to slide down an incline and capturing their motion using high-speed video. Two surfaces were prepared using crystallization of an alkyl ketene dimer (AKD) wax, and the third surface was the leaf of a Lotus (Nelumbo Nucifera). The acceleration of the water droplets on these superhydrophobic surfaces was measured as a function of droplet size and inclination of the surface. For small capillary numbers, we propose that the energy dissipation is dominated by intermittent pinning–depinning transitions at microscopic pinning sites along the trailing contact line of the drop, while at capillary numbers exceeding a critical value, energy dissipation is dominated by circulatory flow in the vicinity of the contacting disc between the droplet and the surface. By combining the results of the droplet acceleration with a theoretical model based on energy dissipation, we have introduced a material-specific coefficient called the superhydrophobic sliding resistance, <i>b</i>_sh. Once determined, this parameter is sufficient for predicting the motion of water drops on superhydrophobic surfaces of a general macroscopic topography. This theory also infers the existence of an equilibrium sliding angle, β_eq, at which the drop acceleration is zero. This angle is decreasing with the radius of the drop and is in quantitative agreement with the measured tilt angles required for a stationary drop to start sliding down an incline

Green Strategy to Reduced Nanographene Oxide through Microwave Assisted Transformation of Cellulose

A green strategy for fabrication of biobased reduced nanographene oxide (r-nGO) was developed. Cellulose derived nanographene oxide (nGO) type carbon nanodots were reduced by microwave assisted hydrothermal treatment with superheated water alone or in the presence of caffeic acid (CA), a green reducing agent. The carbon nanodots, r-nGO and r-nGO-CA, obtained through the two different reaction routes without or with the added reducing agent, were characterized by multiple analytical techniques including FTIR, XPS, Raman, XRD, TGA, TEM, AFM, UV–vis, and DLS to confirm and evaluate the efficiency of the reduction reactions. A significant decrease in oxygen content accompanied by increased number of sp² hybridized functional groups was confirmed in both cases. The synergistic effect of superheated water and reducing agent resulted in the highest C/O ratio and thermal stability, which also supported a more efficient reduction. Interesting optical properties were detected by fluorescence spectroscopy where nGO, r-nGO, and r-nGO-CA all displayed excitation dependent fluorescence behavior. r-nGO-CA and its precursor nGO were evaluated toward osteoblastic cells MG-63 and exhibited nontoxic behavior up to 200 μg mL^–1, which gives promise for utilization in biomedical applications

Understanding the Dispersive Action of Nanocellulose for Carbon Nanomaterials

This work aims at understanding the excellent ability of nanocelluloses to disperse carbon nanomaterials (CNs) in aqueous media to form long-term stable colloidal dispersions without the need for chemical functionalization of the CNs or the use of surfactant. These dispersions are useful for composites with high CN content when seeking water-based, efficient, and green pathways for their preparation. To establish a comprehensive understanding of such dispersion mechanism, colloidal characterization of the dispersions has been combined with surface adhesion measurements using colloidal probe atomic force microscopy (AFM) in aqueous media. AFM results based on model surfaces of graphene and nanocellulose further suggest that there is an association between the nanocellulose and the CN. This association is caused by fluctuations of the counterions on the surface of the nanocellulose inducing dipoles in the sp² carbon lattice surface of the CNs. Furthermore, the charges on the nanocellulose will induce an electrostatic stabilization of the nanocellulose–CN complexes that prevents aggregation. On the basis of this understanding, nanocelluloses with high surface charge density were used to disperse and stabilize carbon nanotubes (CNTs) and reduced graphene oxide particles in water, so that further increases in the dispersion limit of CNTs could be obtained. The dispersion limit reached the value of 75 wt % CNTs and resulted in high electrical conductivity (515 S/cm) and high modulus (14 GPa) of the CNT composite nanopapers

Force Interactions of Nonagglomerating Polylactide Particles Obtained through Covalent Surface Grafting with Hydrophilic Polymers

Nonagglomerating polylactide (PLA) particles with various interaction forces were designed by covalent photografting. PLA particles were surface grafted with hydrophilic poly­(acrylic acid) (PAA) or poly­(acrylamide) (PAAm), and force interactions were determined using colloidal probe atomic force microscopy. Long-range repulsive interactions were detected in the hydrophilic/hydrophilic systems and in the hydrophobic/hydrophilic PLA/PLA-<i>g</i>-PAAm system. In contrast, attractive interactions were observed in the hydrophobic PLA/PLA and in the hydrophobic/hydrophilic PLA/PLA-<i>g</i>-PAA systems. AFM was also used in the tapping mode to determine the surface roughness of both neat and surface-grafted PLA film substrates. The imaging was performed in the dry state as well as in salt solutions of different concentrations. Differences in surface roughness were identified as conformational changes induced by the altered Debye screening length. To understand the origin of the repulsive force, the AFM force profiles were compared to the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory and the Alexander de Gennes (AdG) model. The steric repulsion provided by the different grafted hydrophilic polymers is a useful tool to inhibit agglomeration of polymeric particles. This is a key aspect in many applications of polymer particles, for example in drug delivery

Zero-Dimensional and Highly Oxygenated Graphene Oxide for Multifunctional Poly(lactic acid) Bionanocomposites

The unique strengths of 2D graphene oxide nanosheets (GONSs) in polymer composites are thwarted by nanosheet agglomeration due to strong intersheet attractions. Here, we reveal that shrinking the planar size to 0D graphene oxide quantum dots (GOQDs), together with the intercalation of rich oxygen functional groups, reduces filler aggregation and enhances interfacial interactions with the host polymer. With poly­(lactic acid) (PLA) as a model matrix, atomic force microscopy colloidal probe measurements illustrated that a triple increase in adhesion force to PLA was achieved for GOQDs (234.8 nN) compared to GONSs (80.4 nN), accounting for the excellent exfoliation and dispersion of GOQDs in PLA, in contrast to the notable agglomeration of GONSs. Although present at trace amount (0.05 wt %), GOQDs made a significant contribution to nucleation activity, mechanical strength and ductility, and gas barrier properties of PLA, which contrasted the inferior efficacy of GONSs, accompanied by clear distinction in film transparency (91% and 50%, respectively). Moreover, the GOQDs with higher hydrophilicity accelerated the degradation of PLA by enhancing water erosion, while the GONSs with large sheet surfaces gave a higher hydrolytic resistance. Our findings provide conceptual insights into the importance of the dimensionality and surface chemistry of GO nanostructures in the promising field of bionanocomposites integrating high strength and multifunction (e.g., enhanced transparency, degradation and gas barrier)

Robust and Tailored Wet Adhesion in Biopolymer Thin Films

Model layer-by-layer (LbL) assemblies of poly­(allylamine hydrochloride) (PAH) and hyaluronic acid (HA) were fabricated in order to study their wet adhesive behavior. The film characteristics were investigated to understand the inherent structures during the assembly process. Subsequently, the adhesion of these systems was evaluated to understand the correlation between the structure of the film and the energy required to separate these LbL assemblies. We describe how the conditions of the LbL fabrication can be utilized to control the adhesion between films. The characteristics of the film formation are examined in the absence and presence of salt during the film formation. The dependence on contact time and LbL film thickness on the critical pull-off force and work of adhesion are discussed. Specifically, by introducing sodium chloride (NaCl) in the assembly process, the pull-off forces can be increased by a factor of 10 and the work of adhesion by 2 orders of magnitude. Adjusting both the contact time and the film thickness enables control of the adhesive properties within these limits. Based on these results, we discuss how the fabrication procedure can create tailored adhesive interfaces with properties surpassing analogous systems found in nature