Tuning Wet Adhesion of Weak Polyelectrolyte Multilayers

Weak polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer method are known to become tacky upon contact with water and behave as a viscoelastic fluid, but this wet adhesive property and how it can be modified by external stimuli has not yet been fully explored. We present here a study on the wet adhesive performance of PEMs consisting of branched poly­(ethylene imine) and poly­(acrylic acid) under controlled conditions (e.g., pH, type of salt, and ionic strength) using a 90° peel test. The multilayers demonstrate stick–slip behavior and fail cohesively in nearly all cases. The peel force is the highest at neutral pH, and it decreases in both acidic/basic environments because of inhibited polyelectrolyte mobility. The addition of salts with various metal ions generally reduces the peel force, and this effect tracks with the ionic strength. When transition metal ions are used, their ability to form coordination bonds increases the peel force, with two exceptions (Cu²⁺ and Zn²⁺). With a transition metal ion such as Fe³⁺, the peel force first increases as a function of the concentration and then eventually decreases. The peel force increases proportionally to the peel rate. The films are also characterized via zeta potential (when assembled onto colloidal particles) and shear rheometry. This work provides insight into both the wet adhesive properties of PEMs and the interactions between PEMs and metal ions

Tuning Wet Adhesion of Weak Polyelectrolyte Multilayers

Weak polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer method are known to become tacky upon contact with water and behave as a viscoelastic fluid, but this wet adhesive property and how it can be modified by external stimuli has not yet been fully explored. We present here a study on the wet adhesive performance of PEMs consisting of branched poly­(ethylene imine) and poly­(acrylic acid) under controlled conditions (e.g., pH, type of salt, and ionic strength) using a 90° peel test. The multilayers demonstrate stick–slip behavior and fail cohesively in nearly all cases. The peel force is the highest at neutral pH, and it decreases in both acidic/basic environments because of inhibited polyelectrolyte mobility. The addition of salts with various metal ions generally reduces the peel force, and this effect tracks with the ionic strength. When transition metal ions are used, their ability to form coordination bonds increases the peel force, with two exceptions (Cu²⁺ and Zn²⁺). With a transition metal ion such as Fe³⁺, the peel force first increases as a function of the concentration and then eventually decreases. The peel force increases proportionally to the peel rate. The films are also characterized via zeta potential (when assembled onto colloidal particles) and shear rheometry. This work provides insight into both the wet adhesive properties of PEMs and the interactions between PEMs and metal ions

Tuning Wet Adhesion of Weak Polyelectrolyte Multilayers

Weak polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer method are known to become tacky upon contact with water and behave as a viscoelastic fluid, but this wet adhesive property and how it can be modified by external stimuli has not yet been fully explored. We present here a study on the wet adhesive performance of PEMs consisting of branched poly­(ethylene imine) and poly­(acrylic acid) under controlled conditions (e.g., pH, type of salt, and ionic strength) using a 90° peel test. The multilayers demonstrate stick–slip behavior and fail cohesively in nearly all cases. The peel force is the highest at neutral pH, and it decreases in both acidic/basic environments because of inhibited polyelectrolyte mobility. The addition of salts with various metal ions generally reduces the peel force, and this effect tracks with the ionic strength. When transition metal ions are used, their ability to form coordination bonds increases the peel force, with two exceptions (Cu²⁺ and Zn²⁺). With a transition metal ion such as Fe³⁺, the peel force first increases as a function of the concentration and then eventually decreases. The peel force increases proportionally to the peel rate. The films are also characterized via zeta potential (when assembled onto colloidal particles) and shear rheometry. This work provides insight into both the wet adhesive properties of PEMs and the interactions between PEMs and metal ions

Response of Swelling Behavior of Weak Branched Poly(ethylene imine)/Poly(acrylic acid) Polyelectrolyte Multilayers to Thermal Treatment

Weak polyelectrolyte multilayers (PEMs) prepared by the layer-by-layer technique have attracted a great deal of attention as smart responsive materials for biological and other applications in aqueous medium, but their dynamic behavior as a function of exposure to a wide temperature range is still not well understood. In this work, the thermally dependent swelling behavior of PEMs consisting of branched poly­(ethylenimine) and poly­(acrylic acid) is studied by temperature controlled in situ spectroscopic ellipsometry. Because of diffusion and interpenetration of polyelectrolytes during film deposition, the PEMs densify with increasing bilayer number, which further affects their water uptake behavior. Upon heating to temperatures below 60 °C, the worsened solvent quality of the PEM in water causes deswelling of the PEMs. However, once heated above this critical temperature, the hydrogen bonds within the PEMs are weakened, which allows for chain rearrangement within the film upon cooling, resulting in enhanced water uptake and increased film thickness. The current work provides fundamental insight into the unique dynamic behavior of weak polyelectrolyte multilayers in water at elevated temperatures

Large-Scale Solvent Driven Actuation of Polyelectrolyte Multilayers Based on Modulation of Dynamic Secondary Interactions

Polyelectrolyte multilayers (PEMs), assembled from weak polyelectrolytes, have often been proposed for use as smart or responsive materials. However, such response to chemical stimuli has been limited to aqueous environments with variations in ionic strength or pH. In this work, a large in magnitude and reversible transition in both the swelling/shrinking and the viscoelastic behavior of branched polyethylenimine/poly­(acrylic acid) multilayers was realized in response to exposure with various polar organic solvents (e.g., ethanol, dimethyl sulfoxide, and tetrahydrofuran). The swelling of the PEM decreases with an addition of organic content in the organic solvent/water mixture, and the film contracts without dissolution in pure organic solvent. This large response is due to both the change in dielectric constant of the medium surrounding the film as well as an increase in hydrophobic interactions within the film. The deswelling and shrinking behavior in organic solvent significantly enhances its elasticity, resulting in a stepwise transition from an initially liquid-like film swollen in pure water to a rigid solid in pure organic solvents. This unique and recoverable transition in the swelling/shrinking behaviors and the rheological performances of weak polyelectrolyte multilayer film in organic solvents is much larger than changes due to ionic strength or pH, and it enables large scale actuation of a freestanding PEM. The current study opens a critical pathway toward the development of smart artificial materials

Accelerated Amidization of Branched Poly(ethylenimine)/Poly(acrylic acid) Multilayer Films by Microwave Heating

Chemical cross-linking of layer-by-layer assembled films promotes mechanical stability and robustness in a wide variety of environments, which can be a challenge for polyelectrolyte multilayers in saline environments or for multilayers made from weak polyelectrolytes in environments with extreme pHs. Heating branched poly­(ethylenimine)/poly­(acrylic acid) (BPEI/PAA) multilayers at sufficiently high temperatures drives amidization and dehydration to covalently cross-link the film, but this reaction is rather slow, typically requiring heating for hours for appreciable cross-linking to occur. Here, a more than one order of magnitude increase in the amidization kinetics is realized through microwave heating of BPEI/PAA multilayers on indium tin oxide (ITO)/glass substrates. The cross-linking reaction is tracked using infrared spectroscopic ellipsometry to monitor the development of the cross-linking products. For thick films (∼1500 nm), gradients in cross-link density can be readily identified by infrared ellipsometry. Such gradients in cross-link density are driven by the temperature gradient developed by the localized heating of ITO by microwaves. This significant acceleration of reactions using microwaves to generate a well-defined cross-link network as well as being a simple method for developing graded materials should open new applications for these polymer films and coatings