ABSTRACT
The dewetting dynamics of a supported bilayer polymer thin film on a solid substrate is investigated using grazing incidence x-ray photon correlation spectroscopy. We find that the top layer dewets via the spinodal mechanism. The kinetics of the dewetting is studied by monitoring the time evolution of the surface diffuse x-ray scattering intensity. We study the time evolution of fluctuations about the average surface structure by measuring the two-time x-ray intensity fluctuation correlation functions. Using these two-time correlation functions we quantify the crossover from early-time diffusive dynamics to hydrodynamics. The early diffusive regime satisfies dynamic universality. The two-time correlation functions also quantify the onset of hydrodynamic effects. The hydrodynamic regime is observed during the spinodal dewetting process as these interactions are not screened.
ABSTRACT
We report the origin of the effect of nanoscale confinement on the local viscosity of entangled polystyrene (PS) films at temperatures far above the glass transition temperature. By using marker x-ray photon correlation spectroscopy with gold nanoparticles embedded in the PS films prepared on solid substrates, we have determined the local viscosity as a function of the distance from the polymer-substrate interface. The results show the impact of a very thin adsorbed layer (~7 nm in thickness) even without specific interactions of the polymer with the substrate, overcoming the effect of a surface mobile layer at the air-polymer interface and thereby resulting in a significant increase in the local viscosity as approaching the substrate interface.
ABSTRACT
A method is developed for calculating the small-angle x-ray scattering originating from within the interior of a thin film under grazing incidence illumination. This offers the possibility of using x-ray scattering to probe how the structure of polymers is modified by confinement. When the diffuse scattering from a thin film is measured over a range of incident angles, it is possible to separate the contributions to scattering from the interfaces and the contribution from the film interior. Using the distorted-wave Born approximation the structure factor, S(q), of the film interior can then be obtained. We apply this method to analyze density fluctuations from within the interior of a silicon supported molten polystyrene (PS) film. Measurements were made as a function of film thickness ranging from one to ten times the polymer radius of gyration (Rg). The compressibility, calculated by extrapolating the measured S(q) to q=0, agrees well with that of bulk PS for thick films, but thinner films exhibit a peak in S(q) near q=0. This peak, which grows with decreasing thickness, is attributed to a decreased interpenetration of chains and a consequent enhanced compressibility.
ABSTRACT
By embedding "dilute" gold nanoparticles in single polystyrene thin films as "markers", we probe the local viscosity of the free surface at temperatures far above the glass transition temperature (T(g)). The technique used was x-ray photon correlation spectroscopy with resonance-enhanced x-ray scattering. The results clearly showed the surface viscosity is about 30% lower than the rest of the film. We found that this reduction is strongly associated with chain entanglements at the free surface rather than the reduction in T(g).
ABSTRACT
Polymer nanocomposites offer the potential to create a new type of hybrid material with unique thermal, optical, or electrical properties. Understanding their structure, phase behavior, and dynamics is crucial for realizing such potentials. In this work we provide an experimental insight into the dynamics of such composites in terms of the temperature, wave vector, and volume fraction of nanoparticles, using multispeckle synchrotron x-ray photon correlation spectroscopy measurements on gold nanoparticles embedded in polymethylmethacrylate. Detailed analysis of the intermediate scattering functions reveals possible existence of an intrinsic length scale for dynamic heterogeneity in polymer nanocomposites similar to that seen in other soft materials like colloidal gels and glasses.
ABSTRACT
Overdamped surface capillary wave relaxations on molten polymer films were measured using x-ray photon correlation spectroscopy. We found a transition from a single through a stretched to another single exponential regime as the temperature is decreased from well above to near the bulk glass transition temperature. A universal scaling of the dynamics was discovered over a wide range of film thicknesses, temperatures, and molecular weights (except in the multiple relaxation regime). These observations are justified by hydrodynamic theory and the time-temperature superposition principle by considering an effective viscosity instead of the bulk zero shear viscosity.
ABSTRACT
X-ray diffraction experiments show that solid 4He grown in aerogel is highly polycrystalline, with an hcp crystal structure (as in bulk) and a crystallite size of approximately 100 nm. In contrast to the expectation that the highly disordered solid will have a large supersolid fraction, torsional oscillator measurements show a behavior that is strikingly similar to high purity crystals grown from the superfluid phase. The low temperature supersolid fraction is only approximately 3 x 10(-4), and the onset temperature is approximately 100 mK.
ABSTRACT
Changes to the structure of polystyrene melt films as measured through the spectrum of density fluctuations have been observed as a function of film thickness down to the polymer radius of gyration (Rg). Films thicker than 4Rg show bulklike density fluctuations. Thinner films exhibit a peak in S(q) near q=0 which grows with decreasing thickness. This peak is attributed to a decreased interpenetration of chains resulting in an enhanced compressibility. Measurements were made using small angle x-ray scattering in a standing wave geometry designed to enhance scattering from the interior of the film compared to interface scattering.
ABSTRACT
Carpenter [Phys. Rev. E 61, 532 (2000)] succeeded in determining a single universal model, called the P1 model, that could describe the ellipsometric critical adsorption data from the liquid-vapor interface of four different critical binary liquid mixtures near their critical demixing temperatures. The P1 model also recently has been used to describe neutron reflectometry data from a critical liquid mixture/crystalline quartz interface. However, in another recent study, the P1 model failed to simultaneously describe x-ray reflectometry and ellipsometry data from the liquid-vapor surface of the critical mixture n -dodecane + tetrabromoethane (DT). In this paper, we resolve this discrepancy between x-ray and ellipsometric data for the DT system. At large length scales (far from the interface) the local concentration is described by the P1 model in order to correctly reproduce the temperature dependence of the ellipsometric data. Close to the interface, however, the molecular structure must be correctly accounted for in order to quantitatively explain the x-ray data. An important conclusion that arises from this study is that neutron or x-ray reflectometry is most sensitive to short-range interfacial structure, but may provide misleading information about long-range interfacial structure. Ellipsometry provides a more accurate measure of this long-range interfacial structure. Complex interfacial structures, possessing both short- and long-range structure, are therefore best studied using multiple techniques.
ABSTRACT
Small-angle x-ray scattering (SAXS) was used to measure the microstructure of isotopic mixtures of 3He and 4He adsorbed into silica aerogels as a function of temperature and 3He concentration. The SAXS measurements could be well described by the formation of a nearly pure film of 4He which separates from the bulk mixture onto the aerogel strands and which thickens with decreasing temperature. Previous observations of a superfluid 3He -rich phase are consistent with superfluidity existing within this film phase. Observed differences between different density aerogels are explained in terms of the depletion of 4He from the bulk mixture due to film formation.
ABSTRACT
The surface dynamics of supported ultrathin polystyrene films with thickness comparable to the radius of gyration were investigated by surface sensitive x-ray photon correlation spectroscopy. We show for the first time that the conventional model of capillary waves on a viscous liquid has to be modified to include the effects of a shear modulus in order to explain both static and dynamic scattering data from ultrathin molten polymer films.
ABSTRACT
A small amount of alumina nanoparticles in polymethylmethacrylate causes a sharp depression of the glass transition temperature (Tg) accompanied by a toughening of the composite. We investigated this phenomenon using multispeckle x-ray photon correlation spectroscopy. Measurements reveal a dynamic structure factor that has the form exp[-(t/taua)beta], with beta greater than 1. We show for the first time that beta(T) tracks the internal stress at the polymer-particle interface. The internal stress, which we propose arises due to the entropic penalty that the polymer faces in the presence of the nanoparticles, engenders temporally heterogeneous dynamics. In the jammed glassy state, we show that the dominant fast relaxation mode--taumax--aided by a weak dewetting interface relieves the stress and follows the variations in Tg.
ABSTRACT
The theory for surface dynamics of the thermally excited fluctuations on a homogenous single-layer film of arbitrary depth is generalized to describe surface and interfacial dynamics of polymeric liquid bilayer films in terms of susceptibilities, power spectra, and characteristic relaxation time constants. The effects on surface dynamics originating from viscosity inhomogeneities close to the surface and interfacial regions are investigated by the bilayer theory and compared with the surface dynamics of homogeneous single-layer films under nonslip and slip boundary conditions. Our bilayer theory can also be extended to study interfacial dynamics of more generalized multilayer systems. The effects of viscoelasticity and van der Waals interactions on surface and interfacial dynamics are also briefly discussed.
ABSTRACT
An analysis is presented of how to optimize the experimental beamline configuration for achieving the best possible signal-to-noise ratio (SNR) in X-ray photon correlation spectroscopy experiments using area detectors. It is shown that there exists an optimum detector distance; namely, the highest SNR is achieved by matching the angular pixel size with the angular source size. Binning several pixels together can increase the SNR by permitting to match the shape of a detector pixel to the shape of the source. It is also shown that collimating slits several times wider than the effective transverse coherence length are optimal; further, it is demonstrated that the energy dependence of the SNR is dictated by the energy dependence of detector efficiency and source brilliance. Ultimately the effects of focusing and low longitudinal coherence are discussed.
Subject(s)
Algorithms , Artifacts , Models, Statistical , Spectrum Analysis/methods , Computer Simulation , Photons , Stochastic Processes , X-RaysABSTRACT
We have used direct inversion of x-ray reflectivity data to extract the liquid-vapor interface composition profile and the related critical scaling function of a binary mixture of dodecane and tetrabromoethane. The mixture was in the one-phase region above its critical point. The results indicate the formation of a monolayer of the lower surface tension component followed by an abrupt change to a mixed composition which gradually relaxes to the bulk composition deep within the fluid.
ABSTRACT
We have used measurements of the absolute intensity of diffuse X-ray scattering to extract the interfacial tension of a buried polymer/polymer interface. Diffuse scattering was excited by an X-ray standing wave whose phase was adjusted to have a high intensity at the polymer/polymer interface and simultaneously a node at the polymer/air interface. This method permits the capillary-wave-induced roughness of the interface, and hence the interfacial tension, to be measured independently of the polymer/polymer interdiffusion.
Subject(s)
Algorithms , Models, Chemical , Models, Molecular , Polystyrenes/chemistry , Refractometry/methods , X-Ray Diffraction/methods , Computer Simulation , Polystyrenes/analysis , Scattering, Radiation , Surface PropertiesABSTRACT
The dynamics of supported polymer films were studied by probing the surface height fluctuations as a function of lateral length scale using x-ray photon correlation spectroscopy. Measurements were performed on polystyrene (PS) films of thicknesses varying from 84 to 333 nm at temperatures above the PS glass transition temperature. Within a range of wave vectors spanning 10(-3) to 10(-2) nm(-1), good agreement is found between the measured surface dynamics and the theory of overdamped thermal capillary waves on thin films. Quantitatively, the data can be accounted for using the viscosity of bulk PS.
ABSTRACT
The dynamics of compositional fluctuations in a miscible, entangled homopolymer blend of poly(ethylene oxide) and poly(methyl methacrylate) were studied on length scales smaller than the polymer radii of gyration, and for times comparable to the polymers' disentanglement time. The measured relaxation rates are consistent with predictions of the reptation model, as expressed via the dynamic random-phase approximation. Moreover, the observed mode amplitudes allow for an estimate of the entanglement length in the blend.
ABSTRACT
X-ray photon correlation spectroscopy and small-angle scattering measurements are presented of the dynamics and structure of concentrated suspensions of charge-stabilized polystyrene latex spheres dispersed in glycerol, for volume fractions from 3% to 52%. The static structures of the suspensions show essentially hard-sphere behavior, and the short-time dynamics shows good agreement with predictions for the wave-vector-dependent collective diffusion coefficient. However, the intermediate scattering function is found to violate a scaling behavior found previously for a sterically stabilized hard-sphere suspension.
