The growth of polysaccharide multilayers consisting of positively charged chitosan (CH) and negatively charged heparin (HEP) was monitored in situ by employing a quartz crystal microbalance (QCM-D) and dual-polarization interferometry (DPI). The main focus was on how the physicochemical properties of the solution affect the growth and structure of the resulting multilayer film. These results showed that when increasing the ionic strength of the polysaccharide solutions at a fixed pH, both the "dry" (optical) (DPI) mass and wet (QCM) mass of the adsorbed multilayer film increased. The same effect was found when increasing the pH while keeping the ionic strength constant. Furthermore, the growth of multilayers showed an exponential-like behavior independent of the solution conditions that were used in this study. It was also established that chitosan was the predominant species present in the chitosan-heparin multilayer film. We discuss the viscoelastic properties of the adsorbed layers and their variation during the multilayer buildup. Interestingly and contrary to common interpretation of the QCM-D results, we found that under one particular solution condition (pH 4.2 and 30 mM NaCl) the increase in the dissipation of oscillation energy from the adsorbed layer was a consequence of layer stiffening rather than indicating a more hydrated and viscous film. On the basis of the widely used Voigt viscoelastic model for an adsorbed layer, we show that it is the film viscosity and shear that define the layer viscoelasticity (structure) of the film and not the absolute value of energy dissipation, which in fact can be very misleading.

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An atomic force microscope colloidal probe technique has been employed to probe normal and friction forces between silica surfaces coated with adsorbed layers of a diblock copolymer of the composition poly(N-isopropylacrylamide) 48 -block-poly(3-acrylamidopropyl)trimethylammonium chloride) 20 , abbreviated PNIPAAM 48 -b-PAMPTMA(+) 20 . The interactions between the PNIPAAM 48 -b-PAMPTMA(+) 20 -coated surfaces across a 0.1 mM NaCl (pH 6) solution at 25 C are purely repulsive, due to a combination of steric and electrostatic double-layer forces. However, when the temperature is increased to 35 C, and subsequently to 45 C, an attractive force develops at short separations due to the unfavourable PNIPAAM-water interaction at these temperatures. The temperature-dependent polymer-water interaction has implications for the friction force between the layers. At 25 C a frictional force that increases linearly with increasing load is observed once the surfaces are brought into close contact. At higher temperatures significantly higher friction forces appear as a consequence of attractive segment-segment interactions. Further, a clearly expressed hysteresis between friction forces encountered on loading and unloading is detected. Our results demonstrate that both normal and friction forces between surfaces can be controlled by temperature changes when temperatureresponsive polymers are employed, and friction forces can be adjusted as required from low to high.

Hydrophobicity, and in particular superhydrophobicity, has been extensively considered to promote ice-phobicity. Dynamic contact angle measurements above 0 °C have been widely used to evaluate the water repellency. However, it is the wetting properties of supercooled water at subzero temperatures and the derived work of adhesion that are important for applications dealing with icing. In this work we address this issue by determining the temperature-dependent dynamic contact angle of microliter-sized water droplets on a smooth hydrophobic and a superhydrophobic surface with similar surface chemistry. The data highlight how the work of adhesion of water in the temperature interval from about 25 °C to below −10 °C is affected by surface topography. A marked decrease in contact angle on the superhydrophobic surface is observed with decreasing temperature, and we attribute this to condensation below the dew point. In contrast, no significant wetting transition is observed on the smooth hydrophobic surface. The freezing temperature and the freezing delay time were determined for water droplets resting on a range of surfaces with similar chemistry but different topography, including smooth and rough surfaces in either the Wenzel or the Cassie−Baxter state as characterized by water contact angle measurements at room temperature. We find that the water freezing delay time is not significantly affected by the surface topography and discuss this finding within the classical theory of heterogeneous nucleation.