Soft Nanocomposites--From Interface Control to Interphase Formation.

We report measurements of structure, mechanical properties, glass transition temperature, and contact angle of a novel nanocomposite material consisting of swellable silsesquioxane nanoparticles with grafted poly(ethyl methacrylate) (PEMA) brushes and PEMA matrices with varying molecular weight. We measured the interparticle distance at the surface of the composites using scanning probe microscopy (SPM) and in the bulk of ∼0.5 µm thick films by grazing incidence small angle X-ray scattering (GISAXS). For a given molecular weight of the brush unstable dispersions at high molecular weight of the matrix indicate an intrinsic incompatibility between polymer-grafted-nanoparticles and homopolymer matrices. This incompatibility is affirmed by a high contact angle between the polymer-grafted-nanoparticles and the high molecular weight matrix as measured by SPM. For unstable dispersions, we measured a decreased glass transition temperature along with a decreased plateau modulus by dynamic mechanical thermal analysis (DMTA) which indicates the formation of a liquid-like layer at the brush-matrix interface. This proves the ability to decouple the structural and mechanical properties from the potential to be swollen with small molecules. It opens a new area of use of these soft nanocomposites as slow release materials with tailored mechanical properties.

Nanoscale thermomechanics of wear-resilient polymeric bilayer systems.

We explore the effect of an ultrathin elastic coating to optimize the mechanical stability of an underlying polymer film for nanoscale applications. The coating consists of a several nanometer thin plasma-polymerized norbornene layer. Scanning probes are used to characterize the system in terms of shear-force-induced wear and thermally assisted indentation. The layer transforms a weakly performing polystyrene film into a highly wear-resistive system, ideal for high-density and low-power data storage applications. The result can be understood from the indentation characteristics with a hot and sharp indenter tip. The latter gives rise to a deformation mode in the fully plastic regime, enabling a simple interpretation of the results. The softening transition and the yield stress of the system on a microsecond time scale and a nanometer size scale were obtained. We show that the plastic deformation is governed by yielding in the polystyrene sublayer, which renders the overall system soft for plastic deformation. The ultrathin protection layer contributes as an elastic skin, which shields part of the temperature and pressure and enables the high wear resistance against lateral forces. Moreover, the method of probing polymers at microsecond and nanometer size scales opens up new opportunities for studying polymer physics in a largely unexplored regime. Thus, we find softening temperatures of more than 100 °C above the polystyrene glass transition, which implies that for the short interaction time scales the glassy state of the polymer is preserved up to this temperature.

Electric-field-induced condensation: an extension of the Kelvin equation.

The Kelvin equation relates the vapor pressure of a volatile liquid to the curvature of the liquid surface. It describes phenomena such as capillary condensation, capillary adhesion, nucleation, and the adsorption of vapors into porous media. Here we propose an extension of the Kelvin equation, which takes into account changes of the vapor pressure due to electric fields. The presence of electric fields reduces the saturation vapor pressure and leads to field-induced condensation. Field-induced condensation can explain the presence of water bridges in scanning probe nanolithographic methods such as anodic oxidation.

Nanomechanical properties of advanced plasma polymerized coatings for mechanical data storage.

In this paper we report on the unprecedented deformation behavior of stratified ultrathin polymer films. The mechanical behavior of layered nanoscale films composed of 8-12 nm thin plasma polymerized hexamethyldisiloxane (ppHMDSO) films on a 70 nm thick film of polystyrene was unveiled by atomic force microscopy nanoindentation. In particular, we observed transitions from the deformation of a thin plate under point load to an elastic contact of a paraboloid of revolution, followed by an elastic-plastic contact for polystyrene and finally an elastic contact for silicon. The different deformation modes were identified on the basis of force-penetration data and atomic force microscopy images of residual indents. A clear threshold was observed for the onset of plastic deformation of the films at loads larger than 2 µN. The measured force curves are in agreement with an elastic and elastic-plastic contact mechanics model, taking the amount of deformation and the geometry of the layer that presumably contributed more to the overall deformation into account. This study shows that the complex deformation behavior of advanced soft matter systems with nanoscale dimensions can be successfully unraveled.

Interface roughness of plasma deposited polymer layers.

The interface roughness of adjacent films which were made by plasma polymerization of hexamethyldisiloxane were investigated. Multilayered structures were made by using different plasma conditions in alteration resulting in different mechanical properties within each layer. Scanning force microscopy on the face side of fractured pieces of the multilayer structures revealed a significant phase contrast between the layers. The direct visualization of the interface using the mechanical contrast between layers allowed the estimation of the interfacial roughness. We found that the interfaces between hexamethyldisiloxane films deposited at a radio frequency (RF) input power of 90 W in the presence of oxygen on top of films made by 48 W without oxygen resulted in an interface roughness of ≈10 nm. In the reverse case, a significantly lower interface roughness of ≈3 nm was determined. We attribute the increase of the interfacial roughness compared to the surface roughness being <1 nm to partial etching of the films by the subsequent deposition process. A key role in the appearance of higher interface roughness plays the RF-input power that determines the cross linking density and the hydrocarbon content in layers.

Determination of cross-link density in ion-irradiated polystyrene surfaces from rippling.

The irradiation of polymer surfaces with ion beams leads to pronounced chemical and physical modifications when the ions are scattered at the atoms in the polymer chain. In this way, different products of decomposition occur. Here we show that by changing the ion fluence and the mass of the ion the local mechanical properties as Young's modulus of a polystyrene surface layer can be tailored. By annealing prestretched irradiated PS near the glass transition, surface rippling occurs in the irradiated areas only, which can be described with an elastic model. The moduli obtained from rippling periodicities and elastic model assumptions are in the range between 8 and 800 MPa at the glass transition and characterize the irradiated PS as rubberlike. From these values the network density and the molar mass of entanglement are quantified. The obtained network density equals the density of hydrogen vacancies generated through the scattered ions, as confirmed by simulations of the atomic scattering and displacement processes. The obtained molar mass of entanglement reveals that the PS locally was densely cross-linked. Our results show that even for nondiscrete layered polymer systems relevant polymer parameters can be derived from the well-known surface rippling without the need for costly chemical analysis.