Esben Thormann

Friction in aqueous media tuned by temperature-responsive polymer layers

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 PNIPAAM48-b-PAMPTMA(+)20. The interactions between the PNIPAAM48-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 temperature-responsive polymers are employed, and friction forces can be adjusted as required from low to high.

Interactions between a Polystyrene Particle and Hydrophilic and Hydrophobic Surfaces in Aqueous Solutions

The interaction between a colloidal polystyrene particle mounted on an AFM cantilever and a hydrophilic and a hydrophobic surface in aqueous solution is investigated. Despite the apparent simplicity of these two types of systems a variety of different types of interactions are observed. The system containing the polystyrene particle and a hydrophilic surface shows DLVO-like interactions characteristic of forces between charged surfaces. However, when the surface is hydrophobized the interaction changes dramatically and shows evidence of a bridging air bubble being formed between the particle and the surface. For both sets of systems, plateaus of constant force in the force curves are obtained when the particle is retracted from the surface after being in contact. These events are interpreted as a number of individual polystyrene molecules that are bridging the polystyrene particle and the surface. The plateaus of constant force are expected for pulling a hydrophobic polymer in a bad (hydrophilic) solvent. The plateau heights are found to be of uniform spacing and independent of the type of surface, which suggests a model by which collapsed polymers are extended into the aqueous medium. This model is supported by a full stretching curve showing also the backbone elasticity and a stretching curve obtained in pentanol, where the plateau changes to a nonlinear force response, which is typical for a polymer in a good or neutral solvent. We suggest that these polymer bridges are important in particular for the interaction between polystyrene and the hydrophilic surface, where they to some extent counteract the long-range electrostatic repulsion.

How to measure forces with atomic force microscopy without significant influence from nonlinear optical lever sensitivity

In an atomic force microscope (AFM), the force is normally sensed by measuring the deflection of a cantilever by an optical lever technique. Experimental results show a nonlinear relationship between the detected signal and the actual deflection of the cantilever, which is widely ignored in literature. In this study we have designed experiments to investigate different possible reasons for this nonlinearity and compared the experimental findings with calculations. It is commonly assumed that this nonlinearity only causes problems for extremely large cantilever deflections. However, our results show that the nonlinear detector response might influence many AFM studies where soft or short cantilevers are used. Based on our analysis we draw conclusions of the main reason for the nonlinearity and suggest a rule of thumb for which cantilevers one should use under different experimental conditions.

Adsorption and protein-induced metal release from chromium metal and stainless steel.

A research effort is undertaken to understand the mechanism of metal release from, e.g., inhaled metal particles or metal implants in the presence of proteins. The effect of protein adsorption on the metal release process from oxidized chromium metal surfaces and stainless steel surfaces was therefore examined by quartz crystal microbalance with energy dissipation monitoring (QCM-D) and graphite furnace atomic absorption spectroscopy (GFAAS). Differently charged and sized proteins, relevant for the inhalation and dermal exposure route were chosen including human and bovine serum albumin (HSA, BSA), mucin (BSM), and lysozyme (LYS). The results show that all proteins have high affinities for chromium and stainless steel (AISI 316) when deposited from solutions at pH 4 and at pH 7.4 where the protein adsorbed amount was very similar. Adsorption of albumin and mucin was substantially higher at pH 4 compared to pH 7.4 with approximately monolayer coverage at pH 7.4, whereas lysozyme adsorbed in multilayers at both investigated pH. The protein-surface interaction was strong since proteins were irreversibly adsorbed with respect to rinsing. Due to the passive nature of chromium and stainless steel (AISI 316) surfaces, very low metal release concentrations from the QCM metal surfaces in the presence of proteins were obtained on the time scale of the adsorption experiment. Therefore, metal release studies from massive metal sheets in contact with protein solutions were carried out in parallel. The presence of proteins increased the extent of metals released for chromium metal and stainless steel grades of different microstructure and alloy content, all with passive chromium(III)-rich surface oxides, such as QCM (AISI 316), ferritic (AISI 430), austentic (AISI 304, 316L), and duplex (LDX 2205).

Confinement of linear polymers, surfactants, and particles between interfaces

The review addresses the effect of geometrical confinement on the structure formation of colloidal dispersions like particle suspensions, (non)micellar surfactant solutions, polyelectrolyte solutions and mixed dispersions. The dispersions are entrapped either between two fluid interfaces (foam film) in a Thin Film Pressure Balance (TFPB) or between two solid interfaces in a Colloidal Probe Atomic Force Microscope (Colloidal Probe AFM) or a Surface Force Apparatus (SFA). The oscillating concentration profile in front of the surface leads to an oscillating force during film thinning. It is shown that the characteristic lengths like the distance between particles, the distance between micelles, or the mesh size of the polymer network remain the same during the confining process. The influence of different parameters like ionic strength, molecular structure, and the properties of the outer surfaces on the structure formation are reported. The confinement of mixed dispersions might lead to phase separation and capillary condensation, which in turn causes a pronounced attraction between the two opposing film surfaces.

Protein interactions with bottle-brush polymer layers: Effect of side chain and charge density ratio probed by QCM-D and AFM

Silica surfaces were coated with a range of cationic bottle-brush polymers with 45 units long poly(ethylene oxide) side chains, and their efficiency in reducing protein adsorption was probed by QCM-D, reflectometry and AFM. Preadsorbed layers formed by bottle-brush polymers with different side chain to charge ratio was exposed to two proteins with different net charge, lysozyme and BSA. The reduction in protein adsorption was found to depend on both the type of protein and on the nature of the polyelectrolyte layer. The most pronounced reduction in protein adsorption was achieved when the fraction of charged backbone segments was in the range 0.25-0.5 equivalent to a fraction of poly(ethylene oxide) side chains of 0.75-0.5. It was concluded that these polymers have enough electrostatic attachment points to ensure a strong binding to the surface, and at the same time a sufficient amount of poly(ethylene oxide) side chains to counteract protein adsorption. In contrast, a layer formed by a highly charged polyelectrolyte without side chains was unable to resists protein adsorption. On such a layer the adsorption of negatively charged BSA was strongly enhanced, and positively charged lysozyme adsorbed to a similar extent as to bare silica. AFM colloidal probe force measurement between silica surfaces with preadsorbed layers of bottle-brush polymers were conducted before and after exposure to BSA and lysozyme to gain insight into how proteins were incorporated in the bottle-brush polymer layers.

Force Pulling of Single Cellulose Chains at the Crystalline Cellulose-Liquid Interface : A Molecular Dynamics Study

Pulling single cellulose molecules from a crystalline cellulose surface has been modeled by molecular dynamics (MD) simulations of the experimental procedure used in atomic force microscopy (AFM). Specifically, the aim of the study was to investigate cellulose interactions at desorption. Simulations were performed in both water and the organic solvent cyclohexane. Moreover, the effects of initial octamer conformation and orientation with respect to the surface chains were studied. A strong effect from the solvent was observed. In cyclohexane, normal forces of 200-500 pN and energies of 43.5+/-6.0 kJ/mol glucose unit were required to pull off the octamer. The normal forces in water were substantially lower, around 58 pN, and the energies were 18.2+/-3.6 kJ/mol glucose unit. In addition, the lateral components of the pull-off force were shown to provide information on initial conformation and orientation. Hydrogen bonds between the octamer and surface were analyzed and found to be an important factor in the pull-off behavior. Altogether, it was shown that MD provides detailed information on the desorption processes that may be useful for the interpretation of AFM experiments.

Structural and Nanomechanical Properties of Paperboard Coatings Studied by Peak Force Tapping Atomic Force Microscopy

Paper coating formulations containing starch, latex, and clay were applied to paperboard and have been investigated by scanning electron microscopy and Peak Force tapping atomic force microscopy. A special focus has been on the measurement of the variation of the surface topography and surface material properties with a nanometer scaled spatial resolution. The effects of coating composition and drying conditions were investigated. It is concluded that the air-coating interface of the coating is dominated by close-packed latex particles embedded in a starch matrix and that the spatial distribution of the different components in the coating can be identified due to their variation in material properties. Drying the coating at an elevated temperature compared to room temperature changes the surface morphology and the surface material properties due to partial film formation of latex. However, it is evident that the chosen elevated drying temperature and exposure time is insufficient to ensure complete film formation of the latex which in an end application will be needed.

Toward Homogeneous Nanostructured Polyaniline/Resin Blends

The high interest in applications of conducting polymers, especially polyaniline (PANI), makes it important to overcome limitations for effective usage due to poor processability and solubility. One promising approach is to make blends of PANI in polymeric resins. However, in this approach other problems related to the difficulty of achieving a homogeneous PANI dispersion arise. The present article is focused on this general problem, and we discuss how the synthesis method, choice of dopant and solvent as well as interfacial energies influence the dispersibility. For this purpose, different synthesis methods and dopants have been employed to prepare nanostructures of polyaniline. Dynamic light scattering analysis of dispersions of the synthesized particles in several solvents was employed in order to understand how the choice of solvent affects PANI aggregation. Further information on this subject was achieved by scanning electron microscopy studies of PANI powders dried from various solutions. On the basis of these results, acetone was found to be a suitable dispersion medium for PANI. The polymer matrix used to make the blends in this work is a UV-curing solvent-free resin. Therefore, there is no low molecular weight liquid in the system to facilitate the mixing process and promote formation of homogeneous dispersions. Thus, a good compatibility of the components becomes crucial. For this reason, surface tension and contact angle measurements were utilized for characterizing the surface energy of the PANI particles and the polyester acrylate (PEA) resin, and also for calculating the interfacial energy between these two components that revealed good compatibility within the PANI/PEA blend. A novel technique, based on centrifugal sedimentation analysis, was employed in order to determine the PANI particle size in PEA resin, and high dispersion stability of the PANI/PEA blends was suggested by evaluation of the sedimentation data.

Hyaluronan and phospholipid association in biolubrication

It is becoming increasingly clear that the outstanding lubrication of synovial joints is achieved by a sophisticated hierarchical structure of cartilage combined with synergistic actions of surface-active components present in the synovial fluid. In this work we focus on the association of two components of the synovial fluid, hyaluronan and dipalmitoyl phosphatidyl choline (DPPC), in bulk solution and at interfaces. We demonstrate that hyaluronan associates with DPPC vesicles and adsorbs to supported DPPC bilayers. The association structures formed at the interface are sufficiently stable to allow sequential adsorption of DPPC and hyaluronan, whereby promoting the formation of thick composite layers of these two components. The lubricating ability of such composite layers was probed by the AFM colloidal probe technique and found to be very favorable with low friction coefficients and high load bearing capacity. With DPPC as the last adsorbed component, a friction coefficient of 0.01 was found up to pressures significantly above what is encountered in healthy synovial joints. Hyaluronan as the last added component increases the friction coefficient to 0.03 and decreases the load bearing capacity somewhat (but still above what is needed in the synovial joint). Our data demonstrate that self-assembly structures formed by hyaluronan and phospholipids at interfaces are efficient aqueous lubricants, and it seems plausible that such self-assembly structures contribute to the exceptional lubrication of synovial joints.