Effect of physical ageing in thin glassy polymer films

We have studied the effect of physical ageing in thin supported glassy polystyrene films by using ellipsometry to detect overshooting in the expansivity-temperature curve upon heating of aged samples. Films with thickness 10-200 nm have been aged at 70^° C and 80^° C (below the bulk glass transition temperature). We observe clear relaxation peaks in the expansivity-temperature curve for films thicker than 18 nm but not for the 10 nm film. The intensity of the relaxation peak is inversely proportional to the film thickness, while the temperatures characteristic to the relaxation peak are almost independent of the film thickness. These observations are successfully interpreted by the idea that the surface layer of the order of 10 nm has liquid-like thermal properties. Received 28 October 2002 / Published online: 1 April 2003 RID="a" ID="a"Present address: Yokohama Research Center, Mitsubishi Chemical Corporation, 1000 Kamoshida-chou, Aoba-ku, Yokohama 227-8502, Japan; e-mail: kawana@rc.m-kagaku.co.jp     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Dewetting of thin polymer films

We study the dewetting of thin polymer films deposited on slippery substrate. Recent experiments on these systems have revealed many unexpected features. We develop here a model that takes into account the rheological properties of polymer melts, focussing on two dewetting geometries (the receding of a straight edge, and the opening of a hole). We show that the friction law associated with the slippage between the film and the substrate has a direct influence on the dewetting dynamic. In addition, we demonstrate that residual stresses, which can be stored in the films due to their viscoelasticity, are a source of destabilization for polymer films, and accelerate the dewetting process.     

Spin-cast, thin, glassy polymer films: Highly metastable forms of matter

Ultra thin films of glassy polymers such as polystyrene (PS) can show a) anomalously large thickness changes, b) unexpected dewetting properties, c) large shifts in the glass temperature T_g. The present discussion focusses mainly on point a). A certain cascade of metastable states is presented together with (tentative) explanations. Received 1 March 2001 and Received in final form 10 May 2001     

Surface effects in thin films of antiferroelectric smectic liquid crystals in terms of the short-pitch long-pitch competition model

A theoretical model based on the competition between short-pitch and long-pitch types of helical order is developed for thin films of antiferroelectric smectic liquid crystals. In the case of the “bookshelf” structure of the film and non-polar surfaces, subsurface perturbations of the ordering are found out analytically. Corresponding contributions to the free energies of the different phases are analysed. The possibility of sufficient influence of the boundaries on phase sequences is predicted even in the case of weak surface anchoring. A consistent explanation of the controversial experimental information is given; further ways of experimental justification of the model assumptions are discussed. Received 23 May 2002 RID="a" ID="a"e-mail: mgorkoun@uos.de     

Some relevant parameters affecting the glass transition of supported ultra-thin polymer films

We have measured, the thickness dependence of the glass transition temperature T(g)( h), using ellipsometry at variable temperature, for poly(methyl-methacrylate) (PMMA) of various tacticity in confined geometry. We report that several factors significantly affect T(g)( h): i) polymer microstructure (stereoregularity of PMMA) related to local dynamics; ii) interfacial interactions; iii) conformation of the polymer chains. These results raise many fundamental questions on the origin of the thickness-dependent glass transition. Why and how do the interactions with the substrate significantly affect T(g)( h)? Does T(g)( h) depend on the modifications of conformational parameters of the chains (their entropy)? What is the correlation between local dynamics and T(g)( h) in thin films? The aim of this paper is to summarise these open questions, which should stimulate further investigations in the thin polymer film scientific community.     

Molecular dynamics of hyperbranched polyesters in the confinement of thin films

Broadband Dielectric Spectroscopy is employed to investigate the molecular dynamics in thin films of hyperbranched polyesters (type AB₁B₂, with -OH and -OCOCH₃ as terminal groups). Three relaxation processes are detected: alpha, beta and gamma. While the latter two are not influenced by the confinement, a pronounced effect is observed on the alpha relaxation: with decreasing film thickness the slower relaxation modes of the dynamic glass transition are gradually suppressed, resulting in an increase of the average relaxation rate and in a linear decrease of the dielectric strength. This is attributed to an immobilization in confinement of the polymeric segments located at the periphery of the hyperbranched macromolecular structures.     

Solvent evaporation of spin cast films: “crust” effects

When a glassy polymer film is formed by evaporation, the region near the free surface is polymer rich and becomes glassy first, as noticed long ago by Scriven et al. We discuss the thickness of this “crust” and the time interval where it is present --before freezing of the whole film. We argue that the crust is under mechanical tension, and should form some cracks. This may be the source of the roughness observed on the final, dry films, when the solvent vapor pressure is high (and leads to thin crusts). Received 13 November 2001     

Structure and mechanical properties of low stress tetrahedral amorphous carbon films prepared by pulsed laser deposition

Tetrahedral amorphous carbon films have been produced by pulsed laser deposition, at a wavelength of 248 nm, ablating highly oriented pyrolytic graphite at room temperature, in a 10^-2 Pa vacuum, at fluences ranging between 0.5 and 35 Jcm^-2. Both (100) Si wafers and wafers covered with a SiC polycrystalline interlayer were used as substrates. Film structure was investigated by Raman spectroscopy at different excitation wavelength from 633 nm to 229 nm and by transmission Electron Energy Loss Spectroscopy. The films, which are hydrogen-free, as shown by Fourier Transform Infrared Spectroscopy, undergo a transition from mainly disordered graphitic to up to 80% tetrahedral amorphous carbon (ta-C) above a threshold laser fluence of 5 J cm^-2. By X-ray reflectivity roughness, density and cross-sectional layering of selected samples were studied. Film hardness as high as 70 GPa was obtained by nanoindentation on films deposited with the SiC interlayer. By scratch test film adhesion and friction coefficients between 0.06 and 0.11 were measured. By profilometry we obtained residual stress values not higher than 2 GPa in as-deposited 80% sp³ ta-C films. Received 25 June 2001     

Mobility in thin polymer films ranging from local segmental motion, Rouse modes to whole chain motion: A coupling model consideration

Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( ≈ 1.5 nm) films obtained by intercalating a polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of the local segmental relaxation time found experimentally. Received 1 August 2001 and Received in final form 1 December 2001     

Effect of atmosphere on reductions in the glass transition of thin polystyrene films

We have used nulling ellipsometry to measure the glass transition temperature, T _g , of thin films of polystyrene in ambient, dry nitrogen, and vacuum environments. For all environments, the measured T _g values decrease with decreasing film thickness in a way that is quantitatively similar to previously reported studies in ambient conditions. These results provide strong reinforcement of previous conclusions that such reduced T _g values are an intrinsic property of the confined material. Furthermore, the results are in contrast to recent reports which suggest that the T _g reductions measured by many researchers are the results of artifacts (i.e. degradation of the polymer due to annealing in ambient conditions, or moisture content).     

Dynamic anisotropy and heterogeneity of polystyrene thin films as studied by inelastic neutron scattering

We studied the dynamic anisotropy and heterogeniety of polystyrene thin films in glassy state with inelastic neutorn scattering. Adjusting the scattering vector to the directions parallel and perpendicular to the film surface, we observed the elastic scattering intensities as a function of temperature. It was found for the 200 A film that the elastic intesity decreased with increasing temperature more rapidly in the perpendicular direction than in the pararell direction, showing the higher mobility in the perpendicular direction. However, such dynamical anisotropy was not observed in the 1000 A film. The decrease in the mobility was observed with the film thickness in both the directions. These results were explained in terms of an interface hard layer. We also evelauated the dynamical heterogeniety from the non-Gaussian parameter A0, which increased with decreasing the film thickness, showing the increase in the dynamical heterogeneity. Assuming a simple bi-layer model consisting of the interface hard layer and the bulk-like layer, we analyzed the thickness dependence of the non-Gaussian parameter A0 and the mean square displacement (u2) to find that the hard layer has a thickness of approximately 130 A and a mean square displacement of approximately 0.018 A2 at 230 K.     

Acoustic instabilities in thin polymer films

The spatial confinement of a fluctuation spectrum leads to forces at the confining boundaries. While electromagnetic (EM) fluctuations lead to the well-known dispersion forces, the acoustic analogy has widely been neglected. We show that the strength of the forces resulting from confined acoustic modes may be of the same order of magnitude as van der Waals forces. Additionally, the predicted scaling behavior is identical to the non-retarded case of the EM fluctuations. Our results suggest that dewetting experiments using polymer films are strongly influenced by the acoustic dispersion forces. Received 5 March 2002 and Received in final form 21 May 2002     

Deformation of a tethered polymer in uniform flow

Static properties of a single polymer fixed at one end and subjected to a uniform flow field are investigated for several polymer models: the Gaussian chain, the freely jointed chain, and the FENE (Finitely Extensible Nonlinear Elastic) chain. By taking into account first the excluded-volume interaction and subsequently also the hydrodynamic interaction, the polymer models are gradually completed and the relevance of each effect for the polymer deformation can be identified. Results from computer simulations of these bead spring chains are compared with analytical calculations using either the conformational distribution function or blob models. To this end, in contrast to the blob model with non-draining blobs introduced for a tethered polymer by Brochard-Wyart, we here develop also a model with free-draining blobs. It turns out that a limited extensibility of the polymer – described by nonlinear spring forces in the model – leads to a flow velocity dependence of the end-to-end distance, segment density, etc. which agrees with the power law predictions of the blob model only for very long chains and in a narrow range of flow velocities. This result is important for comparison with recent experiments on DNA molecules which turn out to be still rather short in this respect. The relative importance of finite extensibility, the excluded-volume effect, and hydrodynamic interactions for polymers in flow is not fully understood at present. The simulation of reasonably long chains becomes possible even when fluctuating hydrodynamic interactions are taken into account without employing averaging procedures by introducing efficient numerical approximation schemes. At medium velocity of the uniform flow the polymer is partially uncoiled and simulations show that the effects of excluded-volume and hydrodynamic interactions are position-dependent. Both are stronger near the free end than near the tethered end of the polymer. A crossover from a nearly non-draining polymer at small flow velocities to a free-draining almost uncoiled chain at large velocities is found in the simulations. Accordingly, models assuming the polymer to be composed of either free- or non-draining subunits, like the two blob models, cannot correctly describe the extension and shape of a tethered polymer in flow, and simple power laws for the polymer extension, etc. cannot be expected. Received 21 June 1999     

Preparation and characterization of cobalt-based nanostructured materials

Nano-sized cobalt clusters passivated by alkane-thiol molecules were obtained by the action of concentrated thiol solutions on micrometric cobalt particles. Thiol molecules caused an erosive process on the metal grains with the consequent formation of nano-sized metal debris and cobalt thiolate as by-product. The final material microstructure was composed by cobalt clusters embedded into a continuum cobalt thiolate matrix. Depending on the thiol molecule length, the material texture ranged from rubbery to waxy. These new types of nanocomposite materials were found to be crystalline, thermally stable up to ca. 300 ^°C, intensely red colored, and high hydrophobic. In addition, they generated polymeric structures when dissolved in non-polar solvents. Received 27 September 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: giancaro@unina.it     

Magneto-optical Faraday and Kerr effect of orthoferrite thin films at high temperatures

Orthoferrites present, as bulk materials, reorientation transitions of their magnetic moment alignment at temperatures depending on the rare-earth (RE) ion. In particular, orthoferrites (REFeO₃) with RE = Sm, Dy, present this transition at T _SRT = 443 K and 36 K, respectively. The spectra of the complex Kerr and Faraday angle have been measured on orthoferrite thin films (RE = Sm, Dy, Y), which were prepared by pulsed laser deposition on amorphous quartz substrates. The obtained spectra exhibit contributions of both surfaces and interfaces. Propagation effects of the polarized light in the magneto-optical medium which is interpreted in terms of a simplified theoretical formalism, is also observed. For selected photon energies, temperature dependent Faraday rotation measurements, , on orthoferrite thin films (RE = Sm, Dy, Y) have been performed. A quite different thermal variation compared to the bulk magnetization has been observed. Curie temperatures are found to be close to the bulk values or slightly larger by 10 K to 20 K as in the case of DyFeO₃ and YFeO₃. For RE = Sm and Dy, increases with increasing temperature contrary to the saturation magnetization, passes through a maximum at about 460 K and vanishes with a T _C of 647±18 K, 695 K for RE = Sm and Dy respectively. Received 28 July 2000     

Phase behavior of organic-inorganic crystal

We have investigated the structure and phase behavior of nonmolecularly layered silver stearate by means of temperature-dependent diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. Upon heating the sample, remarkable spectral changes took place. The first phase transition took place that might be associated with a premelting event characterized by the formation of gauche conformers at 390-420 K. A second phase transition took place in which silver nanoparticles with a size of ∼4 nm were formed by thermal decomposition of silver stearate at 520-550 K. These silver nanoparticles, derivatized by stearate, were readily spread as a monolayer at air/water interface, and could be packed in 3-D assemblies by the Langmuir-Blodgett method. Received 29 November 2000     

Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

Heterogeneous dynamics at the glass transition in van der Waals liquids, in the bulk and in thin films

It has been shown over the last few years that the dynamics close to the glass transition is strongly heterogeneous, both by measuring the diffusion coefficient of tagged particles or by NMR studies. Recent experiments have also demonstrated that the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk. We propose here first a thermodynamical model for van der Waals liquids, which accounts for experimental results regarding the bulk modulus of polymer melts and the evolution of the density with temperature. This model allows us to describe the density fluctuations in such van der Waals liquids. Then, by considering the thermally induced density fluctuations in the bulk, we propose that the 3D glass transition is controlled by the percolation of small domains of slow dynamics, which allows to explain the heterogeneous dynamics close to T _g. We show then that these domains percolate at a lower temperature in the quasi-2D case of thin suspended polymer films and we calculate the corresponding glass transition temperature reduction, in quantitative agreement with experimental results of Jones and co-workers. In the case of strongly adsorbed films, we show that the strong adsorption amounts to enhance the slow domains percolation. This effect leads to 1) a broadening of the glass transition and 2) an increase of T _g in quantitative agreement with experimental results. For both strongly and weakly adsorbed films, the shift in T _g is given by a power law, the exponent being the inverse of that of the correlation length of 3D percolation. Received 21 March 2000 and Received in final form 4 December 2000     

Many-body Green's function theory for thin ferromagnetic anisotropic Heisenberg films: treatment of the exchange anisotropy

The many-body Green's function theory developed in our previous work for treating the reorientation of the magnetization of thin ferromagnetic films is extended to include the exchange anisotropy. This leads to additional momentum dependencies which require some non-trivial changes in the formalism. The theory is developed for arbitrary spin values S and for multilayers. The effects of the exchange anisotropy and the single-ion anisotropy, which was treated in our earlier work, on the magnetic properties of thin ferromagnetic films are compared. Received 31 October 2002 Published online 7 May 2003