Ion crater healing and variable temperature ellipsometry as complementary probes for the glass transition in thin polymer films

Poly(methyl methacrylate) (PMMA) thin films of various tacticity and thickness were bombarded at grazing angles by 20 MeV Au ions at different temperatures. The shape of the tracks was investigated by scanning force microscopy (SFM) after annealing for various time at different temperatures and constant quenching rate. The thickness dependent glass transition temperature, T(g)(h), was estimated from the temperature of relaxation of ion-caused nanodeformations in the films. T(g)(h) obtained from the thermal healing of the holes and hillocks is found in good agreement with the one determined by variable temperature ellipsometry for PMMA film thickness of 80 nm and corresponds to the T(g) of each bulk PMMA stereoisomer. Below this thickness, some significant divergences are observed between the T(g) measured by the two techniques. We propose that the healing of ion crater hillock and the kink in the thermal expansion arise from the different nature of chains motions which are perturbed to different extents according to the main polymer chain preferential orientation in the thin film. This can be tentatively interpreted by a so-called "anisotropic" character of the glass transition.     

Dewetting of thin polymer films near the glass transition

Dewetting of ultrathin polymer films near the glass transition exhibits unexpected front morphologies [G. Reiter, Phys. Rev. Lett. 87, 186101 (2001)]. Here, we present the first theoretical attempt to understand these features, focusing on the shear-thinning behavior of these films. We analyze the profile of the dewetting film, and characterize the time evolution of the dry region radius, R(d)(t), and of the rim height, h(m)(t). After a transient time, depending on the initial thickness, h(m)(t) grows like square root[t] while R(d)(t) increases like exp(square root[t]). Different regimes of growth are expected, depending on the initial film thickness and experimental time range.     

Two simultaneous mechanisms causing glass transition temperature reductions in high molecular weight freestanding polymer films as measured by transmission ellipsometry

We study the glass transition in confined polymer films and present the first experimental evidence indicating that two separate mechanisms can act simultaneously on the film to propagate enhanced mobility from the free surface into the material. Using transmission ellipsometry, we have measured the thermal expansion of ultrathin, high molecular-weight (MW), freestanding polystyrene films over an extended temperature range. For two different MWs, we observed two distinct reduced glass transition temperatures (T(g)'s), separated by up to 60 K, within single films with thicknesses h less than 70 nm. The lower transition follows the expected MW dependent, linear T(g)(h) behavior previously seen in high MW freestanding films. We also observe a much stronger upper transition with no MW dependence that exhibits the same T(g)(h) dependence as supported and low MW freestanding polymer films.     

Relation between glass transition temperatures in polymer nanocomposites and polymer thin films

Motivated by recent experiments, we examine within a percolation model whether there is a quantitative equivalence in the glass transition temperatures of polymer thin films and polymer nanocomposites. Our results indicate that, while the qualitative behaviors of these systems are similar, a quantitative equivalence cannot be established in general. However, we propose a phenomenological scaling collapse of our results which suggests a simple framework by which the results of the thin films may be used to quantitatively predict the properties of polymer nanocomposites.     

Heterogeneous nature of the dynamics and glass transition in thin polymer films

Recent experiments have demonstrated that the dynamics in liquids close to and below the glass transition temperature is strongly heterogeneous, on the scale of a few nanometers. We use here a model proposed recently for explaining these features, and show that the heterogeneous nature of the dynamics has important consequences when considering the dynamics of thin films. We show how the dominant relaxation time in a thin film is changed as compared to the bulk, as a function of the thickness, the interaction energy with the substrate, and the temperature. The corresponding time scales cover the so-called VFT (or WLF) regime and vary between 10^-8 s to 10⁴ s typically. In the absence of interaction, our model allows for interpreting suspended films experiments, in the case of small polymers for which the data do not depend on the polymer weight. The interaction leads to an increase of for an interaction per monomer of the order of the thermal energy T. This increase saturates at the value corresponding to strongly interacting films for adsorption energies slightly larger and still of order T. In particular, we predict that the shift can be non-monotonous as a function of the film thickness, in the case of intermediate interaction strength.Received: 1 July 2004, Published online: 26 October 2004PACS: 64.70.Pf Glass transitions - 61.41. + e Polymers, elastomers, and plastics - 68.15. + e Liquid thin films     

Ac-conductivity and dielectric relaxations above glass transition temperature for parylene-C thin films

45% semi-crystalline parylene-C (–H₂C–C₆H₃Cl–CH₂–) _n thin films (5.8 μm) polymers have been investigated by broadband dielectric spectroscopy for temperatures above the glass transition (T _g =90°C). Good insulating properties of parylene-C were obtained until operating temperatures as high as 200°C. Thus, low-frequency conductivities from 10⁻¹⁵ to 10⁻¹² S/cm were obtained for temperatures varying from 90 to 185°C, respectively. This conductivity is at the origin of a significant increase in the dielectric constant at low frequency and at high temperature. As a consequence, Maxwell–Wagner–Sillars (MWS) polarization at the amorphous/crystalline interfaces is put in evidence with activation energy of 1.5 eV. Coupled TGA (Thermogravimetric analysis) and DTA (differential thermal analysis) revealed that the material is stable up to 400°C. This is particularly interesting to integrate this material for new applications as organic field effect transistors (OFETs). Electric conductivity measured at temperatures up to 200°C obeys to the well-known Jonscher law. The plateau observed in the low frequency part of this conductivity is temperature-dependent and follows Arrhenius behavior with activation energy of 0.97 eV (deep traps).     

Reductions of the glass transition temperature in thin polymer films: probing the length scale of cooperative dynamics

We report measurements of the glass transition temperature, T(g), in free standing polymer films in a low M(n) limit where chain confinement effects are not observed. The measured T(g) values are accurately described by a layer model incorporating a mobile surface layer with a size determined by the length scale of cooperative dynamics. The analysis leads to a surface T(g) value and length scale of cooperative motion near bulk T(g) which quantitatively agree with independently determined values. The model and parameters provide a framework within which all previous measurements of T(g) values in thin supported films may be understood and provides values for the length scale of cooperative motion over an extended range of temperatures below the bulk T(g) value.     

Dewetting of thin polymer films at temperatures close to the glass transition

We present detailed studies on dewetting of thin polystyrene (PS) films which were deposited onto silicon wafers coated with a polydimethylsiloxane (PDMS) monolayer. Experiments were performed at temperatures close to the glass transition temperature of PS. Several significant deviations from the dewetting behaviour of Newtonian liquids were observed. The length of the PS molecules, and thus the viscosity, turned out to be of minor importance in determining the dewetting velocity, in particular for the later regimes. In stark contrast, the geometry of the drying spot had a striking influence on the dewetting velocity. Initially, dewetting from straight contact lines proceeded faster than the opening of circular holes. At later stages, the process slowed down significantly in both cases. Under the conditions at which our experiments were performed, PS cannot flow like a simple liquid. Thus, the observed dewetting has to be the consequence of plastic deformation induced by capillary forces. Our results indicate that under such conditions the energy dissipation process is strongly affected by geometry, which is not the case for viscous liquids.Received: 1 January 2003, Published online: 14 October 2003PACS: 68.60.-p Physical properties of thin films, nonelectronic - 61.41. + e Polymers, elastomers, and plastics - 68.55.-a Thin film structure and morphology - 83.50.-v Deformation and flow     

The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films

We present a detailed study of free polymer surfaces and their effects on the measured glass transition temperature (T_g) of thin polystyrene (PS) films. Direct measurements of the near-surface properties of PS films are made by monitoring the embedding of 10 and 20 nm diameter gold spheres into the surface of spin-cast PS films. At a temperature T = 378K( > T_g), the embedding of the spheres is driven by geometrical considerations arising from the wetting of the gold spheres by the PS. At temperatures below T_g ( 363K < T < 370K), both sets of spheres embed 3-4 nm into the PS films and stop. These studies suggest that a liquid-like surface layer exists in glassy PS films and also provide an estimate for the lower bound of the thickness of this layer of 3-4 nm. This qualitative idea is supported by a series of calculations based upon a previously developed theoretical model for the indentation of nanoscale spheres into linear viscoelastic materials. Comparing data with simulations shows that this surface layer has properties similar to those of a bulk sample of PS having a temperature of 374 K. Ellipsometric measurements of the T_g are also performed on thin spin-cast PS films with thicknesses in the range 8nm < h < 290nm. Measurements are performed on thin PS films that have been capped by thermally evaporating 5 nm thick metal (Au and Al) capping layers on top of the polymer. The measured T_g values (as well as polymer metal interface structure) in such samples depend on the metal used as the capping layer, and cast doubt on the general validity of using evaporative deposition to cover the free surface. We also prepared films that were capped by a new non-evaporative procedure. These films were shown to have a T_g that is the same as that of bulk PS (370±1 K) for all film thicknesses measured (> 7 nm). The subsequent removal of the metal layer from these films was shown to restore a thickness-dependent T_g in these samples that was essentially the same as that observed for uncapped PS films. An estimate of the thickness of the liquid-like surface layer was also extracted from the ellipsometry measurements and was found to be 5±1 nm. The combined ellipsometry and embedding studies provide strong evidence for the existence of a liquid-like surface layer in thin glassy PS films. They show that the presence of the free surface is an important parameter in determining the existence of T_g reductions in thin PS films.     

Free surfaces cause reductions in the glass transition temperature of thin polystyrene films

The effect of free surfaces on the glass transition temperature (T(g)) of thin polystyrene films was studied. Measurements were performed on films (8 nm相似文献   

Effect of nanoparticle dispersion on glass transition in thin films of polymer nanocomposites

We present spectroscopic ellipsometry measurements on thin films of polymer nanocomposites consisting of gold nanoparticles embedded in poly(styrene). The temperature dependence of thickness variation is used to estimate the glass transition temperature, T _g . In these thin films we find a significant dependence of T _g on the nature of dispersion of the embedded nanoparticles. Our work thus highlights the crucial role played by the particle polymer interface morphology in determining the glass transition in particular and thermo-mechanical properties of such nanocomposite films.     

Influence of the glass transition on solvent loss from spin-cast glassy polymer thin films

The European Physical Journal E - The interdependence of solvent loss and vitrification in spin-cast poly(methyl methacrylate) thin films is explored. Fast measurements of decreases in film...     

Influence of the glass transition on solvent loss from spin-cast glassy polymer thin films

The interdependence of solvent loss and vitrification in spin-cast poly(methyl methacrylate) thin films is explored. Fast measurements of decreases in film thickness, achieved with ellipsometry, indicate that the rate of solvent (toluene) loss decreases sharply when the solvent volume fraction phi(solv) falls below about 0.15 and the film vitrifies. Ellipsometry and microgravimetry show that solvent is lost from a glassy thin film (150 nm thick) over of a period of more than ten hours, which is much longer than would be required if it was limited by diffusion in the glass. These results support the recently-proposed idea that the compression of the glass creates an energy barrier that slows down solvent loss.     

The glass transition of thin polymer films: some questions,and a possible answer

The European Physical Journal E - A simple and predictive model is put forward explaining the experimentally observed substantial shift of the glass transition temperature, T g, of sufficiently...     

The glass transition of thin polymer films: some questions, and a possible answer

A simple and predictive model is put forward explaining the experimentally observed substantial shift of the glass transition temperature, T_g, of sufficiently thin polymer films. It focuses on the limit of small molecular weight, where geometrical `finite size' effects on the chain conformation can be ruled out. The model is based on the idea that the polymer freezes due to memory effects in the viscoelastic eigenmodes of the film, which are affected by the proximity of the boundaries. The elastic modulus of the polymer at the glass transition turns out to be the only fitting parameter. Quantitative agreement is obtained with our experimental results on short chain polystyrene (M_W = 2 kg/mol), as well as with earlier results obtained with larger molecules. Furthermore, the model naturally accounts for the weak dependence of the shift of T_g upon the molecular weight. It explains why supported films must be thinner than free standing ones to yield the same shift, and why the latter depends upon the chemical properties of the substrate. Generalizations for arbitrary experimental geometries are straightforward.     

Confinement effects on glass transition temperature,transition breadth,and expansivity: Comparison of ellipsometry and fluorescence measurements on polystyrene films

Using ellipsometry, we characterized the nanoconfinement effect on the glass transition temperature (T _gof supported polystyrene (PS) films employing two methods: the intersection of fits to the temperature (Tdependences of rubbery- and glassy-state thicknesses, and the transition mid-point between rubbery- and glassy-state expansivities. The results demonstrate a strong effect of thickness: T_g(bulk)-T_g(23 nm) = 10 ^°\ensuremath T_{{\rm g}}({\rm bulk})-T_{{\rm g}}(23{\,\mbox{nm}})= 10 ^{\circ} C. The T -range needed for accurate measurement increases significantly with decreasing thickness, an effect that arises from the broadening of the transition with confinement and a region below T _g where expansivity slowly decreases with decreasing T . As determined from expansivities, the T _g breadth triples in going from bulk films to a 21-nm-thick film; this broadening of the transition may be a more dramatic effect of confinement than the T _g reduction itself. In contrast, there is little effect of confinement on the rubbery- and glassy-state expansivities. Compared with ellipsometry, T _g ’s from fluorescence agree well in bulk films but yield lower values in nanoconfined films: T _g(bulk) - T _g(23 nm) = 15^° C via fluorescence. This small difference in the T _g confinement effect reflects differences in how fluorescence and ellipsometry report “average T _g ” with confinement. With decreasing nanoscale thickness, fluorescence may slightly overweight the contribution of the free-surface layer while ellipsometry may evenly weight or underweight its contribution.     

Differential AC-chip calorimeter for glass transition measurements in ultra thin polymeric films

A differential AC-chip calorimeter capable to measure the glass transition in nanometer thin films is described. Due to the differential setup pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below one nanogram even above room temperature as needed for the study of the glass transition in nanometer thin polymeric films. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin films of polystyrene (PS) (100–4 nm) and polymethylmethacrylate (PMMA) (400–10 nm) was determined at well defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K) - neither at constant frequency nor for the traces in the activation diagrams (1 Hz–1 kHz).     

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     

Modulus, confinement, and temperature effects on surface capillary wave dynamics in bilayer polymer films near the glass transition

We report relaxation times (τ) for surface capillary waves on 27-127?nm polystyrene (PS) top layers in bilayer films using x-ray photon correlation spectroscopy. At ～10?°C above the PS glass transition temperature (T_{g}), τ tracks with underlayer modulus, being significantly smaller on softer substrates at low in-plane scattering wave vector. Relative to capillary wave theory, we also report stiffening behavior upon nanoconfinement of the PS layers. At PS T_{g}+40?°C, both effects become negligible. We demonstrate how neighboring polymer domains impact dynamics over substantial length scales.