Mean-field theory for polymer adsorption on curved surfaces

We discuss the influence of polymer adsorption on the curvature energy of an interface. Following an article by Clement and Joanny (J. Phys. II 7, 973 (1997)), a mean-field theory is used to calculate the surface tension, rigidity constants and spontaneous curvature associated with both reversible and irreversible polymer adsorption. In the case of irreversible polymer adsorption it is assumed that the amount of adsorbed polymer remains constant upon curving the interface. Unfortunately, constraining the amount of polymer by adding a Lagrange multiplier affects the thermodynamic state of the (free) polymer far away from the interface. Clement and Joanny solve this problem by removing the polymers in the bulk. We allow for the presence of free polymers, but to achieve this we have to apply a local external field to keep the adsorbed amount fixed. The results of the two approaches are compared and a physical interpretation is given. Received 25 July 2001 and Received in final form 5 December 2001     

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     

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     

Effects of entanglement concentration on Tg and local segmental motions

The process of spin-coating to fabricate thin polymer films with high molecular weight can produce samples with entanglement concentrations that are far below the equilibrium value. It is not clear whether or not such low entanglement concentrations are responsible for the depression of the glass temperature in thin polymer films. In this work, we measure the calorimetric glass temperature and viscoelastic response of polystyrenes with molecular weights ranging from 3×10³ to 43.7×10⁶ g/mol, for both bulk material and for samples freeze-dried from dilute solution. We conclude that the reduction of the glass temperature observed in thin polymer films cannot be due to the reduced entanglement concentration in the samples. Received 15 August 2001 and Received in final form 2 March 2002     

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     

Chain segment ordering in lamellar sublayers of block copolymers: A NMR study

The chain segment dynamics in the bulk lamellar phase of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers has been probed by NMR. The experiments were performed on a PS-PDMS diblock and on a PS-PDMS-PS triblock with twice the molecular weight. In the diblock, at room temperature, the PDMS block segments undergo uniaxial reorientations around the normal to the lamellae. In the triblock, the reorientational motions exhibit a lower degree of symmetry: deviations from a uniaxial dynamics are observed. Such a behaviour originates in the anchorage of both PDMS chain ends into the PS glassy layers. Received 27 September 2001 and Received in final form 18 January 2002     

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     

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     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001     

Partitioning of a heterotelechelic polystyrene to separate interfaces of thin films

Heterotelechelic deuteropolystyrenes have been synthesised with a tertiary amine functionality at one end and a fluorocarbon group at the other end of the polymer chain. A layer of this polymer, circa 120 ? thick, has been attached to the surface of a silicon substrate and subsequently covered with a much thicker layer of hydrogenous polystyrene. The combination has then been annealed at 413 K under vacuum for defined times and the subsequent distribution of the deutero heterotelechelic polymer determined using nuclear reaction analysis and neutron reflectometry. The influences of annealing time, molecular weight and thickness of the hydrogenous polymer have been examined. Nuclear reaction analysis showed that an excess of the heterotelechelic polymer formed at both interfaces with a larger excess remaining at the substrate-polymer interface. When the molecular weight of the hydrogenous polymer is lower than that of the deuteropolymer, the deutero layer is initially swollen by the hydrogenous polymer but the thickness then decreases as deutero polymer becomes detached from the silicon substrate and an additional excess layer is eventually formed at the vacuum-polymer surface. When the molecular weight of the hydrogenous polymer is higher, there is an initial shrinkage of the deuteropolymer layer, but the original thickness (∼ radius of gyration of the deuteropolymer) is regained on prolonged annealing. There is no evidence for bridging between the two interfaces by the heterotelechelic polymer. After five days annealing the volume fraction distribution of the deuteropolymer at the silicon substrate was well described by a self-consistent field model where the only adjustable parameter was the sticking energy of the tertiary amine group to the silicon substrate for which a value of 8k _B T was obtained. Comparison of the dependence of the equilibrium layer thickness of the deuteropolymer on the equilibrium grafting density at the silicon surface with the predictions of scaling theory for brush-like polymer layers suggested that the grafted molecules were in the ideal, unperturbed brush region. Received 12 October 2000 and Received in final form 27 March 2001     

Advanced memory effects in the aging of a polymer glass

A new kind of memory effect on low frequency dielectric measurements on plexiglass (PMMA) is described. These measurements show that cooling and heating the sample at constant rate give an hysteretic dependence on temperature of the dielectric constant ε. A temporary stop of cooling produces a downward relaxation of ε. Two main features are observed (i) when cooling is resumed ε goes back to the values obtained without the cooling stop (i.e. the low temperature state is independent of the cooling history) (ii) upon reheating ε keeps the memory of all the cooling stops (Advanced memory). The dependence of this effect on frequency and on the cooling rate is analyzed. The memory deletion is studied too. Finally the results are compared with those of similar experiments done in spin glasses and with the famous experiments of Kovacs. Received 24 September 2001 and Received in final form 20 November 2001     

Drift of a polymer chain in a porous medium --A Monte Carlo study

We investigate the drift of an end-labeled telehelic polymer chain in a frozen disordered medium under the action of a constant force applied to the one end of the macromolecule by means of an off-lattice bead spring Monte Carlo model. The length of the polymers N is varied in the range 8 < N < 128, and the obstacle concentration in the medium C is varied from zero up to the percolation threshold C≈ 0.75. For field intensities below a C-dependent critical field strength B _c, where jamming effects become dominant, we find that the conformational properties of the drifting chains can be interpreted as described by a scaling theory based on Pincus blobs. The variation of drag velocity with C in this interval of field intensities is qualitatively described by the law of Mackie-Meares. The threshold field intensity B _c itself is found to decrease linearly with C. Received 20 August 2001 and Received in final form 19 November 2001     

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.     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

Gels at interfaces

We discuss the adsorption of polymer gels on flat surfaces. Even in cases of complete wetting where the spreading power S is positive and where an equivalent liquid would spread, the elastic stresses due to the gel deformation upon adsorption oppose the spreading. The competition between elasticity characterized by the bulk shear modulus G and capillarity characterized by the spreading power S defines a typical length scale ℓ = S/G for the deformation in the gel. For loose gels ℓ can be of the order of 1 μm. Macroscopic gels larger than ℓ deform only at their edges over a region of size ℓ. Microscopic gels smaller than ℓ show a finite deformation despite the elastic stresses. The elastic stresses limit the spreading of the polymer, but solvent can be sucked out of a swollen gel by wetting the surface. The thin solvent film can extend rather far from the gel edge and carry solvent. We calculate the kinetics of the solvent film formation and of the solvent transfer from a more swollen gel to a less swollen gel. Received 16 July 2001     

Polymer thin films and surfaces: Possible effects of capillary waves

It is discussed how the proximity of a free surface or mobile interface may affect the strain relaxation behavior in a viscoelastic material, such as a polymer melt. The eigenmodes of a viscoelastic film are thus derived, and applied in an attempt to explain the experimentally observed substantial shift of the glass transition temperature of sufficiently thin polymer films with respect to the bulk. Based on the idea that the polymer freezes due to memory effects in the material, and exploiting results from mode-coupling theory, the experimental findings of several independent groups can be accounted for quantitatively, with the elastic modulus at the glass transition temperature as the only fitting parameter. The model is finally applied discussing the possibility of polymer surface melting. A surface molten layer is predicted to exist, with a thickness diverging as the inverse of the reduced temperature. A simple model of thin polymer film freezing emerges which accounts for all features observed experimentally so far. Received 8 August 2001     

Scaling theory of mixed amphiphilic monolayers

We predict the elastic properties of mixed amphiphilic monolayers in the swollen state within the blob model using scaling arguments. First the elastic moduli and the spontaneous curvature of a bimodal brush are determined as a function of the composition and the relative chain length. We obtain simple and useful scaling functions which interpolate between the elastic moduli of a pure short-chain brush and a pure long-chain brush. By using the analogy between block copolymer interfaces and polymeric brushes, the effect of mixing on self-assembled diblock copolymer monolayers is investigated in the swollen state. We calculate various interfacial properties, such as the equilibrium surface coverage, interface curvature, and the mixing free energy as a function of the composition. In general, we find a nonlinear dependence on the composition, which deviates from the simple linear averaging of the properties of pure components. Our results are used to discuss a recent experiment on the effect of amphiphilic block copolymers on the efficiency of microemulsions. Received 29 December 2000 and Received in final form 19 March 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     

Stability of thin polymer films on a corrugated substrate

We study the wetting behaviour of thin polystyrene (PS) films on regularly corrugated silicon substrates. Below a critical film thickness the PS films are unstable and dewet the substrates. The dewetting process leads to the formation of nanoscopic PS channels filling the grooves of the corrugated substrates. Films thicker than the critical thickness appear stable and follow the underlying corrugation pattern. The critical thickness is found to scale with the radius of gyration of the unperturbed polymer chains. Received 6 April 2000 and Received in final form 24 August 2000     

Scaling concepts for polymer brushes and their test with computer simulation

After a brief review of the scaling concepts for static and dynamic properties of polymer brushes in good solvents and Theta solvents, the Monte Carlo evidence is discussed. It is shown that under typical conditions the diameter of the last blob is of the order of 10-20% of the brush height, and therefore pronounced deviations from the self-consistent field predictions occur. In bad solvents, lateral microphase separation occurs leading to an irregular pattern of “dimples”. Particularly interesting is the response of brushes to shear deformation, and the interaction between two interpenetrating brushes. Recent attempts to understand the resulting shear forces via molecular-dynamics simulations are briefly described, and an outlook on related experiments is given. Dedicated to Prof. H.E. Stanley on the occasion of his 60th birthday Received 11 March 2002 and Received in final form 3 June 2002