Thin Supported Polymer Films Research Articles

Confinement effect of inter-arm interactions on glass formation in star polymer melts.

We utilized molecular dynamic simulation to investigate the glass formation of star polymer melts in which the topological complexity is varied by altering the number of star arms (f). Emphasis was placed on how the "confinement effect" of repulsive inter-arm interactions within star polymers influences the thermodynamics and dynamics of star polymer melts. All the characteristic temperatures of glass formation were found to progressively increase with increasing f, but unexpectedly the fragility parameter KVFT was found to decrease with increasing f. As previously observed, stars having more than 5 or 6 arms adopt an average particle-like structure that is more contracted relative to the linear polymer size having the same mass and exhibit a strong tendency for intermolecular and intramolecular segregation. We systematically analyzed how varying f alters collective particle motion, dynamic heterogeneity, the decoupling exponent ζ phenomenologically linking the slow β- and α-relaxation times, and the thermodynamic scaling index γt. Consistent with our hypothesis that the segmental dynamics of many-arm star melts and thin supported polymer films should exhibit similar trends arising from the common feature of high local segmental confinement, we found that ζ increases considerably with increasing f, as found in supported polymer films with decreasing thickness. Furthermore, increasing f led to greatly enhanced elastic heterogeneity, and this phenomenon correlates strongly with changes in ζ and γt. Our observations should be helpful in building a more rational theoretical framework for understanding how molecular topology and geometrical confinement influence the dynamics of glass-forming materials more broadly.

Large T g Shift in Hybrid Bragg Stacks through Interfacial Slowdown.

Studies of glass transition under confinement frequently employ supported polymer thin films, which are known to exhibit different transition temperature Tg close to and far from the interface. Various techniques can selectively probe interfaces, however, often at the expense of sample designs very specific to a single experiment. Here, we show how to translate results on confined thin film Tg to a “nacre-mimetic” clay/polymer Bragg stack, where periodicity allows to limit and tune the number of polymer layers to either one or two. Exceptional lattice coherence multiplies signal manifold, allowing for interface studies with both standard Tg and broadband dynamic measurements. For the monolayer, we not only observe a dramatic increase in Tg (∼ 100 K) but also use X-ray photon correlation spectroscopy (XPCS) to probe platelet dynamics, originating from interfacial slowdown. This is confirmed from the bilayer, which comprises both “bulk-like” and clay/polymer interface contributions, as manifested in two distinct Tg processes. Because the platelet dynamics of monolayers and bilayers are similar, while the segmental dynamics of the latter are found to be much faster, we conclude that XPCS is sensitive to the clay/polymer interface. Thus, large Tg shifts can be engineered and studied once lattice spacing approaches interfacial layer dimensions.

Dynamic heterogeneity and collective motion in star polymer melts.

While glass formation of linear chain polymer melts has widely been explored, comparatively little is known about glass formation in star polymer melts. We study the segmental dynamics of star polymer melts via molecular dynamics simulations and examine the cooperative nature of segmental motion in star melts. In particular, we quantify how the molecular architecture of star polymers, i.e., the number of arms and the length of those arms, affects the glass transition temperature Tg, the non-Gaussian nature of molecular displacements, the collective string-like motion of monomers, and the role of chain connectivity in the cooperative motion. Although varying the number of arms f and the molecular mass Ma of the star arms can significantly influence the average star molecular shape, all our relaxation data can be quantitatively described in a unified way by the string model of glass formation, an activated transport model that derives from the Adam-Gibbs model, where the degree of cooperative motion is identified with the average length L of string-like particle exchange motions observed in our simulations. Previous work has shown the consistency of the string model with simulations of linear polymers at constant volume and constant pressure, as well as for thin supported polymer films and nanocomposites with variable polymer-surface interactions, where there are likewise large mobility gradients as in the star polymer melts studied in the present paper.

The interfacial zone in thin polymer films and around nanoparticles in polymer nanocomposites.

We perform coarse-grained simulations of model unentangled polymer materials to quantify the range over which interfaces alter the structure and dynamics in the vicinity of the interface. We study the interfacial zone around nanoparticles (NPs) in model polymer-NP composites with variable NP diameter, as well as the interfacial zone at the solid substrate and free surface of thin supported polymer films. These interfaces alter both the segmental packing and mobility in an interfacial zone. Variable NP size allows us to gain insight into the effect of boundary curvature, where the film is the limit of zero curvature. We find that the scale for perturbations of the density is relatively small and decreases on cooling for all cases. In other words, the interfaces become more sharply defined on cooling, as naively expected. In contrast, the interfacial mobility scale ξ for both NPs and supported films increases on cooling and is on the order of a few nanometers, regardless of the polymer-interfacial interaction strength. Additionally, the dynamical interfacial scale of the film substrate is consistent with a limiting value for polymer-NP composites as the NP size grows. These findings are based on a simple quantitative model to describe the distance dependence of relaxation that should be applicable to many interfacial polymer materials.

Effect of Adjacent Hydrophilic Polymer Thin Films on Physical Aging and Residual Stress in Thin Films of Poly(butylnorbornene-ran-hydroxyhexafluoroisopropyl norbornene).

The properties of thin supported polymer films can be dramatically impacted by the substrate upon which it resides. A simple way to alter the properties of the substrate (chemistry, rigidity, dynamics) is by coating it with an immiscible polymer. Here we describe how ultrathin (ca. 2 nm) hydrophilic polymer layers of poly(acrylic acid), PAA, and poly(styrenesulfonate), PSS, impact the aging behavior and the residual stress in thin films of poly(butylnorbornene-ran-hydroxyhexafluoroisopropyl norbornene), BuNB-r-HFANB. The aging rate decreases as the film thickness (h) is decreased, but the extent of this change depends on the adjacent layer. Even for the thickest films (h>500 nm), there is a decrease in the aging rate at 100 °C when BuNB-r-HFANB is in contact with PSS. In an effort to understand the origins of these differences in the aging behavior, the elastic modulus and residual stress (σR) in the films were determined by wrinkling as a function of aging time. The change in the elastic modulus during aging does not appear to be directly correlated with the densification or expansion of the films, but the aging rates appear to roughly scale as hσR 1/3. These results illustrate that the physical aging of thin polymer films can be altered by adjacent polymers.

Segmental dynamics of free-standing and supported polymer thin films predicted from a surface-controlled model

Recently, we proposed a surface-controlled cooperative rearranging region (SCC) model that directly predicts the temperature dependence of the cooperativity of segmental dynamics in super-cooled liquids. In this investigation, we employ this model to predict segmental relaxation in polymer ultrathin films. The weighted average of a hole fraction is introduced to account for the cooperativity over segments with different mobilities according to their location in the film. We evaluated the relaxation time for thin films of atactic polystyrene and demonstrated that both the glass transition temperature and the fragility parameter of free-standing and supported films decrease with a reduction of the thickness. This is qualitatively consistent with experimental observations. However, the thickness dependency obtained is weaker compared to that observed experimentally. The origin of this discrepancy is discussed.

Why we need to look beyond the glass transition temperature to characterize the dynamics of thin supported polymer films

There is significant variation in the reported magnitude and even the sign of [Formula: see text] shifts in thin polymer films with nominally the same chemistry, film thickness, and supporting substrate. The implicit assumption is that methods used to estimate [Formula: see text] in bulk materials are relevant for inferring dynamic changes in thin films. To test the validity of this assumption, we perform molecular simulations of a coarse-grained polymer melt supported on an attractive substrate. As observed in many experiments, we find that [Formula: see text] based on thermodynamic criteria (temperature dependence of film height or enthalpy) decreases with decreasing film thickness, regardless of the polymer-substrate interaction strength ε. In contrast, we find that [Formula: see text] based on a dynamic criterion (relaxation of the dynamic structure factor) also decreases with decreasing thickness when ε is relatively weak, but [Formula: see text] increases when ε exceeds the polymer-polymer interaction strength. We show that these qualitatively different trends in [Formula: see text] reflect differing sensitivities to the mobility gradient across the film. Apparently, the slowly relaxing polymer segments in the substrate region make the largest contribution to the shift of [Formula: see text] in the dynamic measurement, but this part of the film contributes less to the thermodynamic estimate of [Formula: see text] Our results emphasize the limitations of using [Formula: see text] to infer changes in the dynamics of polymer thin films. However, we show that the thermodynamic and dynamic estimates of [Formula: see text] can be combined to predict local changes in [Formula: see text] near the substrate, providing a simple method to infer information about the mobility gradient.

Effects of a “bound” substrate layer on the dynamics of supported polymer films

It is widely appreciated that an attractive polymer-substrate interaction can slow relaxation in thin supported polymer films and polymer nanocomposites. Recent measurements and simulations on nancomposites have indicated that this slowing of polymer dynamics occurs more strongly near a highly attractive particle surface where a "bound" layer having a much lower mobility can form, strongly influencing the thermodynamics and dynamics of the film. Here we use molecular simulations to show that a bound interfacial layer having a very similar nature arises in thin supported polymer films when the polymer-polymer attraction is stronger than the polymer-polymer interaction strength. This bound polymer layer effectively insulates the remainder of the film from the strong interfacial interactions, and the resulting thermodynamically determined Tg is relatively insensitive to the polymer-substrate interaction strength when it exceeds that of the polymer-polymer interactions. The presence of this layer gives rise to an additional relaxation process in the self-intermediate scattering function that is not observed in the bulk material and leads to a slowing down of the average relaxation time of the film as a whole. On the other hand, the average relaxation time of the film outside the bound layer does not grow in proportion to the strength of the substrate attraction due to the weak coupling of the substrate relaxation to the relaxation in the interior of the film. At large substrate attraction, the bound layer effectively "cloaks" the substrate, reducing the effect of the polymer-surface interaction on Tg.

Side-group size effects on interfaces and glass formation in supported polymer thin films

Recent studies on glass-forming polymers near interfaces have emphasized the importance of molecular features such as chain stiffness, side-groups, molecular packing, and associated changes in fragility as key factors that govern the magnitude of Tg changes with respect to the bulk in polymer thin films. However, how such molecular features are coupled with substrate and free surface effects on Tg in thin films remains to be fully understood. Here, we employ a chemically specific coarse-grained polymer model for methacrylates to investigate the role of side-group volume on glass formation in bulk polymers and supported thin films. Our results show that bulkier side-groups lead to higher bulk Tg and fragility and are associated with a pronounced free surface effect on overall Tg depression. By probing local Tg within the films, however, we find that the polymers with bulkier side-groups experience a reduced confinement-induced increase in local Tg near a strongly interacting substrate. Further analyses indicate that this is due to the packing frustration of chains near the substrate interface, which lowers the attractive interactions with the substrate and thus lessens the surface-induced reduction in segmental mobility. Our results reveal that the size of the polymer side-group may be a design element that controls the confinement effects induced by the free surface and substrates in supported polymer thin films. Our analyses provide new insights into the factors governing polymer dynamics in bulk and confined environments.

Understanding the Interfacial Mechanical Response of Nanoscale Polymer Thin Films via Nanoindentation

Understanding the mechanical properties of interphase regions in supported polymer thin films is critical as it yields key insights into the constitutive behavior of nanostructured materials. While studies have consistently shown that polymer layers near the substrate exhibit a stiffened response, the size of this region has been reported to vary based on the measurement approach, ranging from hundreds of nanometers in atomic force microscopy (AFM) nanoindentation experiments to a few nanometers in molecular simulations and thin film wrinkling experiments. Here we employ nanoindentation simulations using a coarse-grained molecular dynamics approach to investigate the elastic moduli gradients near the substrate interface of a supported poly(methyl methacrylate) (PMMA) thin film. We find that indenter sizes commonly used in experiments give rise to observed interphase length scales that are larger than the regions in which polymer dynamics are significantly altered as quantified by the segmental molecular s...

A unifying framework to quantify the effects of substrate interactions, stiffness, and roughness on the dynamics of thin supported polymer films.

Changes in the dynamics of supported polymer films in comparison to bulk materials involve a complex convolution of effects, such as substrate interactions, roughness, and compliance, in addition to film thickness. We consider molecular dynamics simulations of substrate-supported, coarse-grained polymer films where these parameters are tuned separately to determine how each of these variables influence the molecular dynamics of thin polymer films. We find that all these variables significantly influence the film dynamics, leading to a seemingly intractable degree of complexity in describing these changes. However, by considering how these constraining variables influence string-like collective motion within the film, we show that all our observations can be understood in a unified and quantitative way. More specifically, the string model for glass-forming liquids implies that the changes in the structural relaxation of these films are governed by the changes in the average length of string-like cooperative motions and this model is confirmed under all conditions considered in our simulations. Ultimately, these changes are parameterized in terms of just the activation enthalpy and entropy for molecular organization, which have predictable dependences on substrate properties and film thickness, offering a promising approach for the rational design of film properties.

Interfacial stiffening of polymer thin films under nanoconfinement

Changes in the mechanical properties of polymer thin films due to substrate and free surfaces determine the performance of soft nanomaterials. Here we systematically investigate how these interfaces influence the elasticity of supported polymer thin films. Our simulation results demonstrate that the substrate–film interfacial interaction has a strong effect on the elastic response of the films, in which the modulus increases with the strength of interfacial interaction with a nonlinear scaling relationship. The investigation of the local stiffness within the film reveals that there exists an interfacial stiffened region near the substrate and a soft region with reduced stiffness near the free surface. Both regions exhibit similar length scales on the order of nanometers. Our analyses explain the molecular origins of recently observed interfacial stiffening and softening phenomena in polymer thin films, and provide a high-resolution description of the local stiffness gradients in polymer thin films.

The Elastic Mechanical Response of Supported Thin Polymer Films

Nanoindentation studies of the mechanical properties of sufficiently thin polymer films, supported by stiff substrates, indicate that the mechanical moduli are generally higher than those of the bulk. This enhancement of the effective modulus, in the thickness range of few hundred nanometers, is indicated to be associated with the propagation and impingement of the indentation tip induced stress field with the rigid underlying substrate; this is the so-called "substrate effect". This behavior has been rationalized completely in terms of the moduli and Poisson's ratios of the individual components, for the systems investigated thus far. Here we show that for thin supported polymer films, in general, information regarding the local chain stiffness and local vibrational constants of the polymers provides an appropriate rationalization of the overall mechanical response of polymers of differing chemical structures and polymer-substrate interactions. Our study should provide impetus for atomistic simulations that carefully account for the role of intermolecular interactions on the mechanical response of supported polymer thin films.

Using Sol–Gel Replications to Assess the Porosity of Block-Copolymer Derived Thin Films

In this paper, we report the use of a sol–gel replication method to prepare high fidelity SiO2 replicas of porous thin films obtained from microphase separated block-copolymer systems as an easy, robust, and rapid way to investigate their inner morphology. The cylinder-forming poly(styrene)-b-poly(lactide) (PS-b-PLA) block copolymer, containing a sacrificial block (PLA), was used to produce porous thin films with thicknesses above one periodical distance and bearing various internal organizations and orientations of the cylinders. The porosity was first infiltrated by silica precursors using a chemical solution deposition process, before being exposed to a brief thermal treatment to provoke inorganic condensation and elimination of the PS template. SEM observations of the obtained replica gave three-dimensional view of the internal topology of the porosity, which were then compared to structural characterizations obtained directly by AFM, SEM, or GISAXS on the parent block-copolymer films. It is shown that the replication provides an ideal tool to characterize the topology of porous networks in supported polymer thin films. This method can be generalized to any type of porous polymer media, offering a unique mode of visualization of the internal topology with valuable details at the substrate interface.

Effect of Water Contact on the Density Distributions of Thin Supported Polymer Films Investigated by an X-ray Reflectivity Method

The diffusion processes of water molecules into polymer films (PMMA/PS homopolymers and random copolymers) in contact with liquid water were investigated using gravimetric methods and X-ray reflectivity (XRR) analysis. Methods of water contact and XRR measurement were designed for studying the systems in the nonequilibrium state of diffusion. Gravimetric measurements confirmed the Fickian diffusion behavior of films in contact with water. Vertical density distributions in PMMA and methylmethacrylate-rich copolymer films demonstrate the existence of a water-rich layer at the interface. However, with further absorption of water into the film, the overall density increased throughout the film. The results suggest that the diffusion of water into the polymer film occurs to recover density uniformity with a high concentration of water molecules at the surface. Some XRR data for the PS- and styrene-rich copolymer films could not be fit and converted to a vertical density distribution because of their huge diffusion coefficients. However, the reflectivity curves for these films and the vertical density distribution after sufficient water contact suggested that the surfaces of these films were commonly diffused after water contact. Atomic force microscopy (AFM) analysis demonstrated that the surface roughness of these films actually increased with water content.

Polarity Effect near the Surface and Interface of Thin Supported Polymer Films: X-ray Reflectivity Study

Four homopolymer films (poly(methyl methacrylate) (PMMA), poly(4-vinylpyridine) (P4VP), polystyrene (PS), and poly(alpha-methyl styrene) (PAMS)) with different interactions with native Si oxide on Si wafers and three random copolymer films (PS-ran-PMMA) with different mole fractions were investigated with the X-ray reflectivity (XRR) method. The electron density profile of each film was obtained by fitting the results of the XRR measurements. A new data correction technique that uses the vertical real beam profile and a fitting method that uses the distorted wave Born approximation were combined to overcome the sensitivity limitations of XRR analysis. The results show that the chemical structures of polymer pendant groups and the interactions between the polymer films and the native Si oxide layer are strongly correlated with the density profiles of the films near the surfaces and interfaces. Two general types of electron density profiles were found that are characterized by the polarity of the pendant group of the polymer. The reproducibility and credibility of the fitting technique were also thoroughly tested.

Temperature-Modulated Ellipsometry: A New Probe for Glass Transition in Thin Supported Polymer Films

Temperature-Modulated Ellipsometry: A New Probe for Glass Transition in Thin Supported Polymer Films

Monolayer Assembly of Oriented Zeolite Crystals on α‐Al2O3 Supported Polymer Thin Films

Monolayer Assembly of Oriented Zeolite Crystals on <i>α</i>‐Al₂O₃ Supported Polymer Thin Films

Vacuum ellipsometry as a method for probing glass transition in thin polymer films

A vacuum ellipsometer has been designed for probing the glass transition in thin supported polymer films. The device is based on the optics of a commercial spectroscopic phase-modulated ellipsometer. A custom-made vacuum chamber evacuated by oil-free pumps, variable temperature optical table, and computer-based data acquisition system was described. The performance of the tool has been demonstrated using 20-200 nm thick poly(methyl methacrylate) and polystyrene films coated on silicon substrates at 10(-6)-10(-8) torr residual gas pressure. Both polymers show pronounced glass transitions. The difficulties in assigning in the glass transition temperature are discussed with respect to the experimental challenges of the measurements in thin polymer films. It is found that the experimental curves can be significantly affected by a residual gas. This effect manifests itself at lower temperatures as a decreased or even negative apparent thermal coefficient of expansion, and is related to the uptake and desorption of water by the samples during temperature scans. It is also found that an ionization gauge--the standard accessory of any high vacuum system--can cause a number of spurious phenomena including drift in the experimental data, roughening of the polymer surface, and film dewetting.

Elastic Properties and Glass Transition of Supported Polymer Thin Films

The present work demonstrates the first application of Brillouin light scattering (BLS) to probe film-guided elastic waves in transparent-substrate supported polymer thin films. In comparison with ...