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     

Viscoelastic dynamics of polymer thin films and surfaces

The strain relaxation behavior in a viscoelastic material, such as a polymer melt, may be strongly affected by the proximity of a free surface or mobile interface. In this paper, the viscoelastic surface modes of the material are discussed with respect to their possible influence on the freezing temperature and dewetting morphology of thin polymer films. In particular, the mode spectrum is connected with mode coupling theory assuming memory effects in the melt. Based on the idea that the polymer freezes due to these memory effects, surface melting is predicted. As a consequence, the substantial shift of the glass transition temperature of thin polymer films with respect to the bulk is naturally explanied. 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. Finally, a simple model is put forward which accounts for the occurrence of certain generic dewetting morphologies in thin liquid polymer films. It demonstrates that by taking into account the viscoelastic properties of the film, a morphological phase diagram may be derived which describes the observed structures of dewetting fronts. It is demonstrated that dewetting morphologies may also serve to determine nanoscale rheological properties of liquids.Received: 1 January 2003, Published online: 14 October 2003PACS: 47.50. + d Non-Newtonian fluid flows - 68.47.Mn Polymer surfaces - 68.60.Dv Thermal stability; thermal effects     

Two-dimensional dynamics of metal nanoparticles on the surface of thin polymer films studied with coherent X rays

X-ray photon-correlation spectroscopy is used to measure the dynamic structure factor f(q,tau) of gold particles moving on the surface of thin polymer films. Above the glass transition of the polymer the peculiar form f(q,tau) approximately exp[-(Gamma tau)(alpha)] is found with 0.7 < alpha < 1.5, depending on sample age and temperature. The relaxation rates Gamma scale linearly with q, excluding a simple Brownian diffusive motion. This type of behavior, already observed in aging bulk soft matter systems, is explained by a power law distribution of particle velocities due to ballistic motion.     

Enthalpy recovery of a glass-forming liquid constrained in a nanoporous matrix: Negative pressure effects

The T _g of organic liquids confined to nanoporous matrices and that of thin polymer films can decrease dramatically from the bulk value. One possible explanation for this phenomenon is the development of hydrostatic tension during vitrification under confinement that results in a concomitant increase in the free volume. Here we present experimental evidence and modeling results for ortho-terphenyl (o-TP) confined in pores as small as 11.6 nm that indicate that, although there is an important hydrostatic tension in the liquid in the pores, it does not develop until near the reduced T _g of the constrained material --well below the bulk T _g. Enthalpy recovery for the o-TP in the nanopores exhibits accelerated physical aging relative to the bulk, as well as a leveling off of the fictive temperature at equilibrium values greater than the aging temperature. An adaptation of the structural recovery model that incorporates vitrification under isochoric conditions is able to provide a quantitative explanation for the apparently anomalous aging observed in nanopore confined liquids and in thin polymeric films. The results strongly support the existence of an intrinsic size effect as the cause of the reduced T _g. Received 3 September 2001     

Charge transfer in thin polymer films of polyarylenephthalides

Transitions from an insulating state to a high-conductivity state are observed in thin polymer films of polyarylenephthalides. The temperature dependences of the conductivity for thin films of wide-band-gap polymer insulators are determined, the relaxation of excess charge is investigated, and the mechanisms of charge transfer in the temperature range preceding the transition to the high-conductivity state are revealed. It is shown that hopping transport over trap states in the band gap is the main mechanism of charge transfer in polyarylenephthalide film.     

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     

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.     

Stability of thermoresponsive methylcellulose thin film: x‐ray reflectivity study

Methylcellulose (MC), a thermoreversible polymer, was fabricated as thin films into silicon substrates and characterized by x‐ray reflectivity (XRR) measurements for its stability with time and heating. XRR data from the as‐is thin films showed good agreement with the single‐layer model on top of a substrate from Parratt's formalism. Data fitting showed that the density of the thin films is slightly higher than the reported value by manufacturers. Interface roughness values indicate good wetting of the polymer onto the substrate. Heating the thin films at the phase transition temperatures and quenching them to room temperature showed no significant changes in the thin film parameters before and after heating. This showed the thermal stability and/or thermoreversibility of the film. Diffuse scattering measurements also showed no significant changes in the lateral structure of the film with heating and quenching. XRR measurements done on fabricated thin films stored for a month showed a slight increase in the film thickness which could be due to the hygroscopic nature of the polymer. Vacuum heating of the stored thin films at 100 °C for 1 h slightly decreased the thickness, but it has been found that other parameters such as density and surface/interface roughness show good thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

Aging phenomena in polystyrene thin films

The aging behavior is investigated for thin films of atactic polystyrene through measurements of complex electric capacitance. During isothermal aging process the real part of the electric capacitance increases with aging time, while the imaginary part decreases with aging time. This result suggests that the aging time dependence of the real and imaginary parts are mainly associated with change in thickness and dielectric permittivity, respectively. In thin films, the thickness depends on thermal history of aging even above the glass transition. Memory and `rejuvenation' effects are also observed in the thin films.     

Editorial: Special issue on Properties of Thin Polymer Films

The behavior of polymers in thin films or close to interfaces is far from being understood. Many observations, encompassing both structural and dynamical behavior, indicate that the properties of polymers in thin films deviate from what we know from the bulk. Questions about the density (irreversible and reversible changes after annealing even above the bulk glass transition temperature), film stability and dewetting, glass transition temperature, diffusion coefficient and chain conformation and relaxation are intensively debated. In particular, it is not yet clear how the size of such chain-like molecules (their molecular weight) comes into play, especially if the thickness of the film is less than the radius of gyration of these macromolecules. In addition, due to the high surface-to-volume ratio the influence of surface and interfacial properties becomes important if not dominant. This interfacial sensitivity highlights the importance of the properties of the near surface region in polymer films; a topic whose importance is beginning to be recognized. This special issue presents experimental and theoretical works on a variety of questions related to polymers at interfaces and in thin films, ranging from space-averaged properties like adhesion to surface ordering or dynamic molecular (segmental) motion in confining geometries. Since the first reports of anomalous dynamics in thin polymer films almost a decade ago, the subject of dynamics in thin films has gained considerable momentum. Until very recently, this body of work focused almost solely on measurements of the thermodynamic signature of the kinetic glass transition. Such measurements are, at best, a very indirect probe of the microscopic dynamics and convolute the temperature dependence, time dependence and sometimes even the thermal history into a single measured value. The articles focusing on dynamics in thin films published in this special issue illustrate an important shift in this rapidly evolving field. There is now a strong focus on many different fronts. Measurements of dynamics are more varied, ranging from indirect studies such as adhesion to direct measurement of the segmental relaxation using dielectric spectroscopy. There is a concerted effort now to draw analogies to bulk systems in order to learn about what effects may contribute to the observation made in thin films. There is also a strong effort using numerical simulations to make quite direct comparisons to measured values in thin films. Finally, in a way that signals a new maturity to this field, a significant fraction of literature being currently published concerns ideas as to why the dynamics in thin films behave the way they do. In this special issue we have aimed at capturing a cross-section of problems of high current interest. While all contributions definitely provide highly valuable insight in the behavior of polymers in thin films, many questions are still unanswered and await further in-depth-going studies. We just want to note a few of these questions, also highlighted in several commentaries published in this issue: Can polymers in experimental studies on thin films ever be fully equilibrated? What is the relaxation behavior of macromolecules in confining geometries with interacting boundaries? How does the relaxation behavior depend on the length scale over which it is measured? What are the mechanical properties of thin polymer films? We tried to assemble different approaches and opinions from various viewpoints. We hope that such a complementary presentation is helpful and stimulates further discussions in order to dissolve some of the confusion in this area, leading eventually to a clear understanding of thin-film properties of polymers. The European Physical Journal E - Soft Matter will continue to provide a forum for the discussion of such questions and a place for the publication of future work on properties of polymers in thin films for all colleagues interested in these questions. Günter Reiter (Editor) James Forrest (Guest Editor)     

Dewetting as an investigative tool for studying properties of thin polymer films

Employing mass conservation, time-resolved dewetting experiments of thin polymer films allow to determine in real time the dynamic contact angle and the slippage length. Moreover, based on a systematic variation of interfacial properties of a polymer brush, dewetting makes it possible to calculate the force it needs to extract a single polymer chain from its own melt. In the visco-elastic regime close to the glass transition, the temperature and molecular weight dependence of the relaxation time of residual stresses resulting from film preparation by spin-coating can be obtained from the evolution of the shape of the dewetting rim. The presented examples demonstrate that dewetting represents a powerful approach for a sensitive characterization of rheological, frictional and interfacial properties of thin polymer films.     

Thickness dependence of electrical properties of ITO film deposited on a plastic substrate by RF magnetron sputtering

Indium tin oxide (ITO) films with various thicknesses in range of 40-280 nm were prepared onto a plastic substrate (PMMA). Deposition was carried out with RF magnetron sputtering method and the substrate temperature was held at ∼70 °C, in lack of the thermal damage to the polymer substrate. Changes in microstructure and electrical properties of ITO films according to their thicknesses were investigated. It was found that amorphous layer with thickness of 80 nm was formed at the interface on the polymer substrate and polycrystalline ITO could be obtained above the thickness. Conductivity of ITO films was found to be strongly dependent on the crystallinity. Consequently, it is suggested that crystallinity of the deposited films should be enhanced at the initial stage of deposition and the thickness of amorphous region be reduced in order to prepare high quality ITO thin films on polymer substrates.     

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     

In Situ Characterisation of Polymer Surfaces and Thin Organic Films in Plasma Processing

In situ sampling techniques are presented for investigation of plasma surface modification of polymers and plasma polymerisation. FTIR spectroscopy (infrared absorption reflection spectroscopy - IRRAS, and attenuated total reflection - ATR) are properly used for characterisation of the changes in the molecular structure of thin polymer films (polystyrene, polyethylene) due to low pressure plasma treatment. The thin films were prepared by dip or spin coating procedures. In the case of plasma polymerisation a novel fibre-ATR technique is applied to investigate the plasma polymerisation process in the plasma bulk. Results are exemplary shown for plasma polymerisation of styrene. Ellipsometric measurements allowed the characterisation of the thin plasma modified top polymer surface layer or thin deposited plasma polymer films by their refractive index and thickness. It was shown that the applied surface plasmon ellipsometry is very sensitive with respect to the usual ellipsometry for investigation of polymer surface modification. The in situ microgravimetry by means of electronic vacuum microbalance permitted to measure the change of the sample mass in the order of 1 μg during the plasma treatment. The first steps in plasma modification (concurrence between the incorporation of plasma particles and the material etching) were studied.     

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.     

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.     

Investigation of the linear electro-optic effect for the guest–host polymer DR13/PEK-c thin films

The polyetherketone (PEK-c) guest–host polymer thin films doped with disperse red 13 were prepared by spin-coating method. The corona poling condition was optimized by the poling profiles. The polymer films were poled by corona-onset poling at elevated temperature, and the corona poling setup includes a grid voltage making the surface-charge distribution uniform. The linear electro-optic coefficients of the poled polymer films have been determined at λ=632.8 nm by using a new simple interferometric technique, which is based on compensating the change of the optical length due to the electro-optic effect of the poled polymer film by the anti-piezoelectric effect of a quartz crystal.