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.     

Pressure, temperature, and thickness dependence of CO2-induced devitrification of polymer films

The glass transition temperature is known to increase with decreasing film thickness h for sufficiently thin poly(methyl methacrylate) films supported by silicon oxide substrates. We show that this system undergoes a CO2 pressure-induced devitrification transition, P(g), which is film thickness dependent, P(g)(h)=DeltaP(g)+P(bulk)(g). P(bulk)(g) is the bulk glass transition and DeltaP(g) can be positive or negative depending on T and P. The phenomenon of retrograde vitrification, wherein the polymer exhibits a rubbery-to-glassy-to-rubbery transition upon changing temperature isobarically, is also shown to occur in this system and it is film thickness dependent.     

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.     

Intramicellar glass transition and liquid dynamics in soft confinement

We explore the dynamics of viscous propylene glycol (PG) near its glass transition for the case of soft spatial confinement. The supercooled liquid is geometrically restricted by the reverse micelles of a glass-forming PG/AOT/decalin microemulsion, with the intramicellar dynamics being probed by triplet state solvation dynamics. While hard confinement by porous solids is known to result in slower dynamics and an increased glass transition temperature T(g) of PG, the nanodroplets suspended in a more fluid environment display faster structural relaxation, equivalent to a reduction of T(g) as observed in freestanding polymer films.     

Glass transition temperature of freely-standing films of atactic poly(methyl methacrylate)

We have used ellipsometry to measure the glass transition temperature T(g) of high molecular weight (M(w)=790 x 10(3)), freely-standing films of atactic poly(methyl methacrylate) (a-PMMA), as well as films of the same polymer supported on two different substrates: the native oxide layer of silicon (Si) and gold-covered Si. We observe linear reductions in T(g) with decreasing film thickness h for the freely-standing PMMA films with 30 nm < h<100 nm, which is qualitatively similar to previous results obtained for freely-standing polystyrene (PS) films. However the magnitude of the T(g) reductions for PMMA is much less than for freely-standing films of PS of comparable molecular weight and thickness. We also find that for films supported on either substrate, with thicknesses as small as 30 nm, the T(g) values do not deviate substantially from the value measured for thick films.     

Molecular mobility in polymer thin films

Fluorescence recovery after photobleaching was used to measure in-plane dye-probe diffusion coefficients, D, in thin films of monodisperse polystyrene supported on fused quartz substrates. The substrates were prepared with a high density of surface hydroxyl groups which interact favorably with repeat units of the polymer. The effects of temperature and film thickness were investigated, at temperatures above the bulk glass transition of the polymer, T(g), and in the range of film thicknesses from 1-10(2) times the radius of gyration (R(g)) of individual polymer molecules. As the film thickness decreases towards R(g) the value of D increases above the bulk values, with significant effects first appearing in films approximately 20R(g). In the thinnest films studied, about 4R(g), the values of D lie as much as two orders over bulk values. At the same time, the temperature dependence of D becomes much weaker than in bulk. Analysis by free volume theory indicates that apparent values of both T(g) and the thermal expansion coefficient for liquid state, alpha(L), decrease as the film thickness decreases. The possible effects of surface segregation of the dye probe are discussed.     

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   

Shear modulation force microscopy study of near surface glass transition temperatures

We report results of glass transition (T(g)) measurements for polymer thin films using atomic force microscopy (AFM). The AFM mode, shear modulation force microscopy (SMFM), involves measuring the temperature-dependent shear force on a tip modulated parallel to the sample surface. Using this method we have measured the surface T(g) of thin (17-500 nm) polymer films and found that T(g) is independent of film thickness (t>17 nm), strength of substrate interactions, or even presence of substrate.     

Molecular simulation of ultrathin polymeric films near the glass transition

Properties such as the glass transition temperature ( T(g)) and the diffusion coefficient of ultrathin polymeric films are shown to depend on the dimensions of the system. In this work, a hard-sphere molecular dynamics methodology has been applied to simulate such systems. We investigate the influence that substrates have on the behavior of thin polymer films; we report evidence suggesting that, depending on the strength of substrate-polymer interactions, the glass transition temperature for a thin film can be significantly lower or higher than that of the bulk.     

First inelastic neutron scattering studies on thin free standing polymer films

Glass transition studies in free standing polymer films have revealed values of the transition temperature, T(g), which were substantially reduced below the bulk for sufficiently thin films. Here we report on the preparation of two stacks of free standing polystyrene films: 70 films with a thickness of h approximately 107 nm and 140 films with h approximately 55 nm with equivalent total sample thicknesses of approximately 7.5 microm. We have performed the first measurements on such samples using inelastic neutron scattering, and demonstrate that inelastic neutron scattering experiments, performed on the time-of-flight spectrometer IN6 and the backscattering spectrometer IN16 at the Institut Laue-Langevin, are feasible.     

Hydrophobic switching nature of methylcellulose ultra-thin films: thickness and annealing effects

We have studied the thermosensitive property of methylcellulose (MC) thin films supported on Si substrate by static sessile drop contact angle measurements, and their surface properties and thin film structure by x-ray reflectivity (XRR) and atomic force microscopy (AFM) techniques. From the static sessile drop contact angle measurements, the MC thin films showed the characteristic hydrophilic-to-hydrophobic transition at ～70?°C, which is the lower critical solution temperature of the bulk solution volume phase separation transition. For films with thickness d ≤ R(g), the onset of such a transition is affected by the film thickness while very thick films, d ? R(g), yielded higher contact angles. Annealing the MC thin films with thicknesses ～200 ? (near the radius of gyration, R(g), of the polymer) below the bulk glass transition temperature (T(g) ～ 195?° C) would not change the hydrophobic switch nature of the film but annealing 'at' and above the bulk T(g) would change its surface property. From surface topography images by AFM, there were no significant changes in either the roughness or the film texture before and after annealing. With XRR data, we were able to determine that such changes in the surface properties are highly correlated to the film thickness changes after the annealing process. This study, we believe, is the first to examine the thermal annealing affects on the thermal response function of a thermoresponsive polymer and is important for researching how to tailor the hydrophobic switching property of MC thin films for future sensing applications.     

Dielectric relaxations in ultrathin isotactic PMMA films and PS-PMMA-PS trilayer films

The local and cooperative dynamics of supported ultrathin films ( L = 6.4 - 120 nm) of isotactic poly(methyl methacrylate) (i-PMMA, Mn = 118 x 10(3) g/mol) was studied using dielectric relaxation spectroscopy for a wide range of frequencies (0.1 Hz to 10(6) Hz) and temperatures (250 - 423 K). To assess the influence of the PMMA film surfaces on the glass transition dynamics, two different sample geometries were employed: a single layer PMMA film with the film surfaces in direct contact with aluminum films which act as attractive, hard boundaries; and a stacked polystyrene-PMMA-polystyrene trilayer film which contains diffuse PMMA-PS interfaces. For single layer films of i-PMMA, a decrease of the glass transition temperature T(g) by up to 10 K was observed for a film thickness L < 25 nm (comparable to R(EE)), indicated by a decrease of the peak temperature T(alpha) in the loss epsilon(")(T) at low and high frequencies and by a decrease in the temperature corresponding to the maximum in the apparent activation energy E(a)(T) of the alpha-process. In contrast, measurements of i-PMMA sandwiched between PS-layers revealed a slight (up to 5 K) increase in T(g) for PMMA film thickness values less than 30 nm. The slowing down of the glass transition dynamics for the thinnest PMMA films is consistent with an increased contribution from the less mobile PMMA-PS interdiffusion regions.     

Evidence for a nodeless gap from the superfluid density of optimally doped Pr(1.855)Ce(0.145)CuO(4-y) films

We present measurements of the ab-plane magnetic penetration depth, lambda(T), in five optimally doped Pr(1.855)Ce(0.145)CuO(4-y) films for 1.6 K< or =T < or =T(c) approximately 24 K. Low resistivities, high superfluid densities n(s)(T) proportional, variant lambda(-2)(T), high T(c)'s, and small transition widths are reproducible and indicative of excellent film quality. For all five films, lambda(-2)(T)/lambda(-2)(0) at low T is well fitted by an exponential temperature dependence with a gap, Delta(min), of 0.85k(B)T(c). This behavior is consistent with a nodeless gap and is incompatible with d-wave superconductivity.     

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.     

Dielectric investigation of the temperature dependence of the nonexponentiality of the dynamics of polymer melts

Using broad band dielectric spectroscopy (10(-5)-10(9) Hz), combining time domain and frequency domain techniques, we study the temperature dependence of the non-Debye character of the alpha relaxation of polymer melts in the glass transition temperature T(g) range. The alpha relaxation process is described in terms of the Kohlrausch-Williams-Watts relaxation function which has a single parameter beta to characterize the nonexponentiality of the relaxation. At high temperatures, beta remains nearly insensitive to temperature changes, whereas in the vicinity of T(g) a nearly linear increasing of beta with temperature is found. The temperature range where the change of the beta(T) behavior occurs is located for all the polymers investigated around 1.2T(g). Moreover, our results indicate a common value of beta approximately equal to 1/3 at the temperature where the relaxation time diverges. The beta(T) behavior near T(g) is discussed in terms of a "rugged landscape" phase space which allows us to rationalize both the beta(T) behavior observed as well as the similarities of our findings near T(g) with the results reported in simulations on Ising spin glasses and other model systems.     

Effect of pressure on the secondary relaxation in a simple glass former

We have studied dielectric spectra of the glass-forming liquid metafluoroaniline under hydrostatic pressure up to 700 MPa. Its glass transition pressure p(g) increases approximately linearly with temperature. Above p(g)(T), a well pronounced secondary relaxation, the Johari beta peak, is observed showing activated behavior. The activation energy rises proportionally to pressure and, consequently, proportionally to the glass transition temperature T(g)(p). The activation volume is independent of temperature but exhibits different values for pressures higher and lower than the pressure where the liquid left the ergodic regime. The activation volumes are about 1/10 and 1/6 of the molecular volume of fluoroaniline, respectively, suggesting that there are two different species of clusters.     

Investigation of transition States in bulk and freestanding film polymer glasses

We have performed transition state searches on the potential energy landscape for bulk and freestanding film polymer glasses and identified connected minima. An analysis of the displacements between minima shows that the sites that undergo the greatest displacement are highly localized in space for both the bulk and the thin-film systems studied. In the case of the thin film, the clusters originate at the surface and penetrate into the center of the film thereby coupling the relaxation in the center of the film to the mobile surface layer. Furthermore, the energy barriers between minima are lower in the thin film than in the bulk system. These findings can rationalize the experimentally observed depression of the glass transition temperature in freestanding polymer films.     

Glass transitions and dynamics in thin polymer films: dielectric relaxation of thin films of polystyrene

The glass transition temperature T(g) and the temperature T(alpha) corresponding to the peak in the dielectric loss due to the alpha process have been simultaneously determined as functions of film thickness d through dielectric measurements for polystyrene thin films supported on glass substrate. The dielectric loss peaks have also been investigated as functions of frequency for a given temperature. A decrease in T(g) was observed with decreasing film thickness, while T(alpha) was found to remain almost constant for d>d(c) and to decrease drastically with decreasing d for d相似文献   

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.