Thermal evolution of a polymer-nanoparticle binary mixture.

We experimentally probe the microscopic variations in a model polymer-nanoparticle (NP) binary mixture (mixture of polybutadiene and clay nanoplatelets) across a thermal evolution path for which Tevolution > Tg(polymer). The evolution of the NP dispersion, NP crystallinity, polymer chain-NP interface, and nature of polymer chain-NP interaction are mapped for a spectrum of temperatures and NP concentrations constrained by experiments. Multiple pieces of evidence indicate that thermal evolution does not influence the nature of interparticle dispersion and is also independent of NP concentration in the binary mixture. However, the NP crystalline order significantly reduces across the thermal evolution path. Thermal evolution induces a transition of a sharp polymer chain-NP interface to a diffuse interfacial layer. In contrast, an already diffuse polymer-NP interface existing in the binary mixture due to particle crowding at high NP concentrations undergoes no significant change in its nature across the evolution path. At all particle concentrations, thermal evolution changes the dominant interaction from polymer chain-polymer chain to polymer chain-NP. These insights aid in explaining the molecular origins of unique and anomalous behaviors shown by polymer-nanoparticle binary mixtures while undergoing thermal evolution.

Nanoparticles can modulate network topological defects during multimodal elastomer formation.

We experimentally show that nanoparticles (NPs) can significantly regulate the network topological defects during a molecularly controlled elastomeric synthesis. Using positron annihilation lifetime spectroscopy, we demonstrate this on well-defined model systems of poly(dimethyl siloxane) elastomers and layered silicate nanoparticles (NPs). The evolutions of topological defects in elastomeric networks prepared from unimodal, bimodal, and NP dispersed bimodal elastomers are sequentially investigated. The extent of NP induced defect regulation is identified by varying the particle concentration from moderately low to an approximate upper limit. The fraction of free volume hole defects present between packed chains in the network generated by molecular control is significantly reduced. The fraction of smaller interstitial cavities near the cross-link sites shows a moderate increase at the lowest NP concentration. However, this fraction decreases at a high NP concentration and is nearly the same as that of bimodal networks that are devoid of NP infusion. Despite the variations in their fractions with NP infusion, the sizes of both these types of defects that remain in the network are minimally affected. The collective topological defects arising from chain induced heterogeneity also show a qualitative reduction upon NP infusion.

Hydration influences on the phase heterogeneity of segmented copolymers.

We elucidate the influences of hydration on the morphological heterogeneity of the class of hard-soft segmented copolymers by experimenting on three model members selected from this group. For influences on phase segmentation, we quantify the degree of phase separation, segment boundary diffusiveness and extent of interphase mixing. Qualitative variations induced by hydration in hydrogen bonding within the phases are also mapped. An inverse relationship between the degree of segmentation and inherent water miscibility of the polymer backbones is observed, that is, high miscibility reducing the degree of segmentation, whereas poor miscibility increasing it. We then quantify hydration induced variations in the size, volume fraction and interaction pair potentials of individual hard segments. The influences on hard segment assemblies are assessed by quantifying their size, volume fraction, interaction pair potential and intrasegment adhesion. This quantification reveals a complex interplay between the volume expansion of individual hard segments and simultaneous swelling and disassembly of their assemblies. Finally, we integrate the segmentation parameters with observed alterations in hydrogen bonding and the inherent polarizability of segments to present a mechanism that reasonably describes the hydrated state morphology. Besides revealing the influences of hydration on the morphological heterogeneity of this class of polymers, our insights give strategies for new synthesis methods for water contact applications and aids in predicting their hydration induced thermomechanical property alterations.

Unraveling the Polymer Chain-Adsorbed Constrained Interfacial Region on an Atomistically Thin Carbon Sheet.

Confinement of graphene and its functional derivatives in synthetic and biomacromolecules has been widely demonstrated recently to manifest in several multiscale phenomena in their mixtures. However, the intricate adsorbed interfacial region formed between polymer chains and a single layer of atomistically thin carbon sheet hitherto evaded an understanding of its nature and characteristics. Here, we reveal the structure of this constrained region and estimate the thickness of the adsorbed polymer layer on a single layer of an atomistically thin graphene oxide sheet using both direct experiments and molecular dynamics simulations. We use small-angle neutron scattering on a model multicomponent mixture formed by an adsorbing polymer, graphene oxide, and solvent for revealing the structure of the constrained interfacial region. We quantify the intricate adsorbed polymer layer thickness on a single layer of atomistically thin graphene oxide sheet by Euclidean approximation of the experimentally observed self-similar interfacial structure. The state of polymer chain random walk and influence of unadsorbed chains under experimental conditions are investigated and juxtaposed against the accuracy of this quantification. For long-chain polymers, the adsorbed layer thickness increases with increasing polymer molecular weight and shows a scaling relationship δ ∼ Rg0.22 with the polymer radius of gyration. For short-chain polymers, the thickness is nearly independent of molecular weight and shows a scaling relationship δ ∼ 0.6 Rg0.22. Coarse-grained molecular dynamics simulations performed on a model system similar to experiments qualitatively ratify the experimentally observed molecular weight-thickness relationship. Simulations show no discernible scaling relationship between radius of gyration and adsorbed layer thickness for low-molecular-weight polymers but show a consistent scaling δ ∼ Rg for high-molecular-weight polymers. A comparison between results from experiments and simulations indicates a discerning pathway in deciphering interface-governed multiscale phenomena in mixtures of adsorbing macromolecules with graphene and its functional derivatives.

Deducing Multiple Interfacial Dynamics during Polymeric Foaming.

Several interfacial phenomena are active during polymeric foaming, the dynamics of which significantly influence terminal stability, cell structure, and in turn the thermomechanical properties of temporally evolved foam. Understanding these dynamics is important in achieving desired foam properties. Here, we introduce a method to simultaneously portray the time evolution of bubble growth, lamella thinning, and plateau border drainage, occurring during reactive polymeric foaming. In this method, we initially conduct bulk and surface shear rheology under polymerizing and nonfoaming conditions. In a subsequent step, foaming experiments were conducted in a rheometer. The microscopic structural dimensions pertaining to the terminal values of the dynamics of each interfacial phenomena are then measured using a combination of scanning electron microscopy, optical microscopy, and imaging ellipsometry, after the foaming is over. The measured surface and bulk rheological parameters are incorporated in time evolution equations that are derived from mass and momentum transport occurring when a model viscoelastic fluid is foamed by gas dispersion. Analytical and numerical solutions to these equations portray the dynamics. We demonstrate this method for a series of reactive polyurethane foams generated from different chemical sources. The effectiveness of our method is in simultaneously obtaining these dynamics that are difficult to directly monitor because of short active durations over multiple length scales.

Solvent transport through hard-soft segmented polymer nanocomposites.

We conducted transport studies of a common solvent (toluene) in its condensed state, through a model hard-soft segmented polyurethane-clay nanocomposite. The solvent diffusivity is observed to be non-monotonic in a functional relationship with a filler volume fraction. In stark contrast, both classical tortuous path theory based geometric calculations and free volume measurements suggest the normally expected monotonic decrease in diffusivity with increase in clay volume fraction. Large deviations between experimentally observed diffusivity coefficients and those theoretically estimated from geometric theory are also observed. However, the equilibrium swelling of a nanocomposite as indicated by the solubility coefficient did not change. To gain an insight into the solvent interaction behavior, we conducted a pre- and post swollen segmented phase analysis of pure polymers and nanocomposites. We find that in a nanocomposite, the solvent has to interact with a filler altered hard-soft segmented morphology. In the altered phase separated morphology, the spatial distribution of thermodynamically segmented hard blocks in the continuous soft matrix becomes a strong function of filler concentration. Upon solvent interaction, this spatial distribution gets reoriented due to sorption and de-clustering. The results indicate strong non-barrier influences of nanoscale fillers dispersed in phase segmented block co-polymers, affecting solvent diffusivity through them. Based on pre- and post swollen morphological observations, we postulate a possible mechanism for the non-monotonic behaviour of solvent transport for hard-soft segmented co-polymers, in which the thermodynamic phase separation is influenced by the filler.

Polymeric foaming with nanoscale nucleants: a surface nanobubble mechanism.

The dimensionally restricted, diffusion-driven volumetric change of almost flat nucleated surface nanobubbles hosted on dispersed nanoscale surfaces is proposed as the probable mechanism of heterogeneous bubble generation during polymer-nanoscale-nucleant suspension foaming. By conducting numerical simulations, this hypothesis is used to predict the final bubble sizes upon polymeric foaming with nanoscale nucleants and to compare them with reported experimentally determined values. The volumetric change in the bubble hosted on the miniscule surface is envisaged to occur due to two parallel diffusion processes: 1) through the contact line of the bubble cap with the surface, and 2) through the curved gas-polymer interface. The foaming conditions determine the direction and molar rate of both these diffusions. The mechanism explains the relative nucleating efficiency of nanoscale surfaces experimentally observed during reactive and nonreactive polymeric foaming by predicting the growth or dissolution of the bubble. In the case of nonreactive thermoplastic foaming, the size of the bubbles released to the bulk from the nanoscale surface varies in a near linear fashion with respect to the size of the nucleants, limited to a maximum nucleant size. Beyond this maximum, the size of bubble generated is independent of the nucleant size. However, increase in the initial nanoscopic contact angle does not significantly affect the bubble size upon detachment from the surface.

Thermally tailored gradient topography surface on elastomeric thin films.

We report a simple method for creating a nanopatterned surface with continuous variation in feature height on an elastomeric thin film. The technique is based on imprinting the surface of a film of thermo-curable elastomer (Sylgard 184), which has continuous variation in cross-linking density introduced by means of differential heating. This results in variation of viscoelasticity across the length of the surface and the film exhibits differential partial relaxation after imprinting with a flexible stamp and subjecting it to an externally applied stress for a transient duration. An intrinsic perfect negative replica of the stamp pattern is initially created over the entire film surface as long as the external force remains active. After the external force is withdrawn, there is partial relaxation of the applied stresses, which is manifested as reduction in amplitude of the imprinted features. Due to the spatial viscoelasticity gradient, the extent of stress relaxation induced feature height reduction varies across the length of the film (L), resulting in a surface with a gradient topography with progressively varying feature heights (hF). The steepness of the gradient can be controlled by varying the temperature gradient as well as the duration of precuring of the film prior to imprinting. The method has also been utilized for fabricating wettability gradient surfaces using a high aspect ratio biomimetic stamp. The use of a flexible stamp allows the technique to be extended for creating a gradient topography on nonplanar surfaces as well. We also show that the gradient surfaces with regular structures can be used in combinatorial studies related to pattern directed dewetting.

Modeling diffusion in foamed polymer nanocomposites.

Two-way multicomponent diffusion processes in polymeric nanocomposite foams, where the condensed phase is nanoscopically reinforced with impermeable fillers, are investigated. The diffusion process involves simultaneous outward permeation of the components of the dispersed gas phase and inward diffusion of atmospheric air. The transient variation in thermal conductivity of foam is used as the macroscopic property to track the compositional variations of the dispersed gases due to the diffusion process. In the continuum approach adopted, the unsteady-state diffusion process is combined with tortuosity theory. The simulations conducted at ambient temperature reveal distinct regimes of diffusion processes in the nanocomposite foams owing to the reduction in the gas-transport rate induced by nanofillers. Simulations at a higher temperature are also conducted and the predictions are compared with experimentally determined thermal conductivities under accelerated diffusion conditions for polyurethane foams reinforced with clay nanoplatelets of varying individual lamellar dimensions. Intermittent measurements of foam thermal conductivity are performed while the accelerated diffusion proceeded. The predictions under accelerated diffusion conditions show good agreement with experimentally measured thermal conductivities for nanocomposite foams reinforced with low and medium aspect-ratios fillers. The model shows higher deviations for foams with fillers that have a high aspect ratio.

Lithographic Tuning of Polymeric Thin Film Surfaces by Stress Relaxation.

We report a facile soft lithography (SL) technique that allows fabrication of patterned polymeric surfaces with feature height varying between 0 and h0, using a single stamp. The method relies on the partial relaxation of the applied stress in a viscoelastic polymer thin film imprinted under a transient external load using a flexible stamp. The applicability of the technique is demonstrated for thermosetting (rubbery) as well as thermoplastic (glassy) polymers over a wide range of lateral dimensions. The lateral dimension and the periodicity of imprinted patterns remain identical to that of the original stamp. The method has potential applications in creating templates for performing combinatorial experiments related to wetting and dewetting studies, adhesion, nanotribology, microfluidics, etc.

Probing nanodispersions of clays for reactive foaming.

Nanodispersions of clays in polyurethane components have been prepared. Nanoclays (both natural and organically modified) of various aspect ratios are used. The fillers are dispersed separately in polyurethane components, viz., polyol and polyisocyanate. The nanodispersions are characterized by the combined use of solution rheology, X-ray scattering, cryo-electron microscopy, and IR spectroscopy. Reactive foaming of these nanodispersions is carried out to make polyurethane nanocomposite foams. The status of the dispersion of fillers in components and in foams has been compared to investigate the effect of the foaming process in exfoliation. Interpretation of the results from different characterization techniques describes the state of the dispersion of fillers in components and in foam. The rheological and physicochemical behaviors of nanodispersions are shown to have a significant influence on the properties of nanocomposite foams.