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.     

Deviations from liquidlike behavior in molten polymer films at interfaces

We have performed x-ray specular and diffuse scattering on liquid polymer films and analyzed the spectra as a function of film thickness and molecular weight. The results show that films whose molecular weight is close to the entanglement length behave as simple liquids except that the shortest wavelength is determined by the radius of gyration (R(g)) rather than the monomer-monomer distance. When the molecular weight is higher than the entanglement length, the strong deviations from liquidlike behavior are observed. We find that the long wavelength cutoff vector, q(l,c), scales with film thickness, d as d(-1.1+/-0.1) rather than the usual d(-2) expected for simple liquids. If we assume that these deviations are due to surface pinning of the polymer chains, then our results are consistent with the formalism developed by Fredrickson et al. to explain the capillary wave spectrum that can propagate in a polymer brush.     

Instabilities and coarsening of stressed crystal surfaces in aqueous solution

Strong pattern formation occurs on polished miscut surfaces of sodium chlorate (NaClO3) single crystals that are uniaxially stressed perpendicular to the step edge direction and placed in a saturated aqueous solution. The wavelength lambda of the stress-induced surface instability increased continuously in experiments up to 9 days after placed in the solution. There were three successive regimes of coarsening: (i) one-dimensional step bunching with lambda approximately t(1/4) until an undulation transition was reached, (ii) a two-dimensional coarsening mechanism with lambda approximately t(1/2), and a gradual transition to (iii) Ostwald ripening-like coarsening with lambda approximately t(1/3). The coarsening of the surface patterns towards a stable, flat surface implies the spontaneous formation of a stress-free skin on the surface of the stressed solid.     

Laser-induced pattern formation in liquid sulfur

Liquid sulfur is a well-known liquid which exhibits a polymerization transition at T_p=159 °C. Recently, it was found from our experiments that such a transition can be induced below T_p through laser illumination and that an iridescent pattern appears under strong illumination with a pulsed laser of more than 60 mJ/cm² pulse. It is proposed that the visible change in iridescence is due to a macroscopic reconstruction of laser-generated polymers and that a laser-induced phase transition takes place from a freely expanded polymer phase to an ordered polymer phase when increasing the laser illumination. To further examine this possibility, the time variation of the iridescent pattern has been fully investigated using a macro lens, a polarized microscope and an optical microscope. In an analysis of the iridescent pattern, a rapid decrease in the area was observed after an initial slow decrease, suggesting a type of phase transition. Results from the observation of a quenched sulfur sample with a polarized microscope gave evidence that the iridescent region consists of polymers. Through observation of the liquid with a microscope, a striped pattern with micrometer sized spacing was noted in the iridescent pattern. A drastic color change was observed in the pattern from its generation to its disappearance. Sample thickness dependence of the pattern was also observed. These results were well explained by assuming the self-arrangement of laser-generated colloidal polymers.     

Density-fluctuation-induced swelling of polymer thin films in carbon dioxide

We report an anomalous swelling of polymer thin films in carbon dioxide (CO(2)) which is associated (in both locus and form) with the density fluctuation ridge that forms along the extension of the coexistence curve of gas and liquid in the P-T phase diagram. Neutron reflectivity results showed that CO(2) could be sorbed to a large extent ( approximately 60%) in thin polymer films even when the bulk miscibility of the polymer with CO(2) is very poor. The anomalous swelling is found to scale with the polymer radius of gyration (R(g)) and extends to a distance approximately 10 R(g).     

Evolution of particle-scale dynamics in an aging clay suspension

Multispeckle x-ray photon correlation spectroscopy was employed to characterize the slow dynamics of a suspension of highly charged, nanometer-sized disks. At wave vectors q corresponding to interparticle length scales, the dynamic structure factor follows a form f(q,t) approximately exp([-(t/tau)(beta)], where beta approximately 1.5. The relaxation time tau increases with the sample age t(a) approximately as tau approximately t(1.8)(a) and decreases with q as tau approximately q(-1). Such behavior is consistent with models that describe the dynamics in disordered elastic media in terms of strain from random, local structural rearrangements. The measured amplitude of f(q,t) varies with q in a manner that implies caged particle motion. The decrease in the range of this motion and an increase in suspension conductivity with increasing t(a) indicate a growth in interparticle repulsion as the mechanism for internal stress development implied by these models.     

Photoinduced Structural Changes in Poly(4-Vinyl Pyridine): A Luminescence Study

In the present work we show a way of controlling photoluminescence (PL) properties through photoinduced quasi-crystal formation in a system based on poly(4-vinyl pyridine) (P4VPy). Under UV irradiation at 380 nm, concentrated solutions of P4VPy in pyridine turn into gel. This phase transition results in changes in the optical properties of this polymer. The position of the PL maximum can be changed continuously from 440 to 480 nm during irradiation. After several minutes of UV irradiation a new red-shifted PL at 492 nm appears upon excitation by light of a wavelength corresponding to that of the initial PL maximum, which is also red-shifted during irradiation. Solutions of P4VPy in pyrimidine show similar behavior, but those in pyridazine do not exhibit such behavior. We have found that the reason for the observed changes in the electronic properties is a photoinduced directional ordering of polymer molecules in a special quasi-crystal formation. The process originates from a structural change in the side chain of P4VPy, namely, protonation of the polymeric pyridine after solvation. During irradiation, the polymeric pyridinium ion interacts with neutral polymeric pyridine molecules. Interchain interaction through hydrogen bonds lead to an electronic property change. We observed that the process of photoinduced sol-gel transformation is reversible. Mechanical perturbation or heating can convert the gel back to a fluid solution. The red-shifted PL is not observed, and the initial PL is blue-shifted to 450 nm and stays there.     

Replica field theory for a polymer in random media

In this paper we revisit the problem of a (non-self-avoiding) polymer chain in a random medium which was previously investigated by Edwards and Muthukumar (EM) [J. Chem. Phys. 89, 2435 (1988)]. As noticed by Cates and Ball (CB) [J. Phys. (France) 49, 2009 (1988)] there is a discrepancy between the predictions of the replica calculation of EM and the expectation that in an infinite medium the quenched and annealed results should coincide (for a chain that is free to move) and a long polymer should always collapse. CB argued that only in a finite volume one might see a "localization transition" (or crossover) from a stretched to a collapsed chain in three spatial dimensions. Here we carry out the replica calculation in the presence of an additional confining harmonic potential that mimics the effect of a finite volume. Using a variational scheme with five variational parameters we derive analytically for d<4 the result R approximately (g|ln &mgr;|)(-1/(4-d)) approximately (g ln V)(-1/(4-d)), where R is the radius of gyration, g is the strength of the disorder, &mgr; is the spring constant associated with the confining potential, and V is the associated effective volume of the system. Thus the EM result is recovered with their constant replaced by ln V as argued by CB. We see that in the strict infinite volume limit the polymer always collapses, but for finite volume a transition from a stretched to a collapsed form might be observed as a function of the strength of the disorder. For d<2 and for large V>V' approximately exp(g(2/(2-d))L((4-d)/(2-d))) the annealed results are recovered and R approximately (Lg)(1/(d-2)), where L is the length of the polymer. Hence the polymer also collapses in the large L limit. The one-step replica symmetry breaking solution is crucial for obtaining the above results.     

Similarity of the signatures of the initial stages of phase separation in metastable and unstable polymer blends

Time-resolved small angle neutron scattering was used to probe the initial stages of liquid-liquid phase separation in both critical and off-critical binary polymer blends, and the critical (q(c)) and most probable (q(m)) wave vectors were identified for several quench depths. For the critical blend, the Cahn-Hilliard-Cook theory provides a framework for analyzing the data and explains the observed decrease in q(m) with time. For the off-critical blend, q(m) is independent of quench time, regardless of whether the quench is metastable or unstable.     

Optical magnetoelectric effect in the polar GaFeO3 ferrimagnet

The optical magnetoelectric (ME) effect, i.e., the change of optical absorption upon the reversal of the light propagation direction, has been investigated for a polar ferrimagnet GaFeO3. For dipole- and spin-forbidden d-d transition bands located at 1.2-2.3 eV, a clear signal of the optical ME effect (Deltaalphat approximately 3x10(-3)) is observed with an applied magnetic field as low as 500 Oe and a sample thickness (t) of 50 microm. The observation of a large ME effect in the present compound suggests a possible route to magnification of this novel phenomenon for application.     

Tunable face-centered-cubic photonic crystal formed in holographic polymer dispersed liquid crystals

We report on the fabrication and electro-optic measurements of face-centered-cubic (fcc) lattices in holographic polymer dispersed liquid-crystal materials. Four linearly polarized coherent plane waves were interfered to generate a fcc optical lattice that was subsequently and indefinitely recorded as an arrayed pattern of nanometer-sized liquid-crystal droplets (approximately 50 nm) at lattice nodes within a polymer matrix. Observed transmission spectra and Kossel diffraction curves are consistent with fcc crystal structure. A completely reversible 2% wavelength shift of the (+/- 111) stop band was observed on application of an electric field.     

Structure of growing networks with preferential linking

The model of growing networks with the preferential attachment of new links is generalized to include initial attractiveness of sites. We find the exact form of the stationary distribution of the number of incoming links of sites in the limit of long times, P(q), and the long-time limit of the average connectivity q(s,t) of a site s at time t (one site is added per unit of time). At long times, P(q) approximately q(-gamma) at q-->infinity and q(s,t) approximately (s/t)(-beta) at s/t-->0, where the exponent gamma varies from 2 to infinity depending on the initial attractiveness of sites. We show that the relation beta(gamma-1) = 1 between the exponents is universal.     

NO2分子在440～495 nm范围内的激光诱导荧光激发谱

以 NdYAG脉冲激光器泵浦的光学参量发生器/放大器作激发光源, 获得了室温、低气压条件下, NO2分子在440～495 nm波长范围内的激光诱导荧光激发谱, 将所得谱线峰归属为NO2由基电子态X2A1态向第二电子激发态B2B1态的跃迁, 利用实验所得峰值波长计算了NO2分子B2B1态的角振动频率ωe. 通过对NO2分子B2B1→X2A1跃迁的荧光时间分辨光谱进行实验研究, 得到15 Pa气压下B2B1(0, 9, 0)振动态的能级寿命τ=49 μs. 测量了荧光寿命随气压的变化关系, 利用曲线拟合得到NO2 B2B1(0, 9, 0)振动态的自发辐射寿命τ0≈55 μs和无辐射跃迁弛豫速率常数. kq=1.2×10-9 cm3 molecule-1s-1.     

Oscillations due to two-electron exchange during He-Ne collisions

Ne (-)(1s(2)2s(2)2p(5)3s(2)) and He (-)(1s2s(2)) autodetachment peaks in electron spectra arising from He-Ne collisions at energies ranging from 350 eV to 6 keV have been measured. The areas of these two peaks are found to oscillate approximately in antiphase, with a constant wavelength, on a (velocity)(-1) scale. It is shown that this behavior can be explained by the "quasiresonance" situation for the separating particles in the channels Ne (-)-He (+) and He (-)-Ne (+). This explanation implies that the oscillations can be understood as being due to the simultaneous "hopping" of two electrons.     

Characteristics of driven polymer surfaces: growth and roughness

Using a Monte Carlo simulation, the growth and roughness characteristics of polymer surfaces are studied in 2+1 dimensions. Kink-jump and reptation dynamics are used to move polymer chains under a driving field where they deposit onto an impenetrable attractive wall. Effects of field (E), chain length (L(c)), and the substrate size (L) on the growing surfaces are studied. In low field, the interface width (W) shows a crossover from one power-law growth in time (W approximately t(beta(1))) to another (W approximately t(beta(2))), before reaching its asymptotic value (W(s)), with beta(1)( approximately 0.5+/-0.1)相似文献   

Effects of the screening breakdown in the diffusion-limited aggregation model

Several models based on the diffusion-limited aggregation (DLA) model were proposed and their scaling properties explored by computational and theoretical approaches. In this paper, we consider a new extension of the on-lattice DLA model in which the unitary random steps are replaced by random flights of fixed length. This procedure reduces the screening for particle penetration present in the original DLA model and, consequently, generates new pattern classes. The patterns have DLA-like scaling properties at small length of the random flights. However, as the flight size increases, the patterns are initially round and compact but become fractal for sufficiently large clusters. Their radius of gyration and number of particles at the cluster surface scale asymptotically as in the original DLA model. The transition between compact and fractal patterns is characterized by wavelength selection, and 1/k noise was observed far from the transition.Received: 2 March 2004, Published online: 14 December 2004PACS: 05.40.Fb Random walks and Levy flights - 05.50. + q Lattice theory and statistics (Ising, Potts, etc.) - 05.10.Ln Monte Carlo methods     

Surface wetting of liquid nanodroplets: droplet-size effects

The spreading of liquid nanodroplets of different initial radii R0 is studied using molecular dynamics simulation. Results for two distinct systems, Pb on Cu(111), which is nonwetting, and a coarse-grained polymer model, which wets the surface, are presented for Pb droplets ranging in size from approximately 55,000 to 220,000 atoms and polymer droplets ranging in size from approximately 200,000 to 780 000 monomers. In both cases, a precursor foot precedes the spreading of the main droplet. This precursor foot spreads as r(2)(f)(t) = 2D(eff)t with an effective diffusion constant that exhibits a droplet-size dependence D(eff) approximately R(1/2)(0). The radius of the main droplet r(b)(t) approximately R(4/5)(0) is in agreement with kinetic models for the cylindrical geometry studied.     

Coexistence and criticality in size-asymmetric hard-core electrolytes

Liquid-vapor coexistence curves and critical parameters for hard-core 1:1 electrolyte models with diameter ratios lambda = sigma(-)/sigma(+) = 1 to 5.7 have been studied by fine-discretization Monte Carlo methods. Normalizing via the length scale sigma(+/-) = 1 / 2(sigma(+)+sigma(-)), relevant for the low densities in question, both T(*)(c) ( = k(B)T(c)sigma(+/-)/q(2)) and rho(*)(c) ( = rho(c)sigma(3)(+/-)) decrease rapidly (from approximately 0.05 to 0.03 and 0.08 to 0.04, respectively) as lambda increases. These trends, which unequivocally contradict current theories, are closely mirrored by results for tightly tethered dipolar dimers (with T(*)(c) lower by approximately 0%-11% and rho(*)(c) greater by 37%-12%).     

Global nature of dilute-to-dense transition of granular flows in a 2D channel

The dilute-to-dense transition of granular flow of particle size d(0) is studied experimentally in a two-dimensional channel (width D) with confined exit (width d). Our results show that with fixed d and D there is a maximum inflow rate Q(c) above which the flow changes from dilute to dense and the outflow rate drops abruptly from Q(c) to a dense rate Q(d). A rescaled critical rate q(c) is found to be a function of a scaling variable lambda only: q(c) approximately F(lambda), where lambda identical with d/d(0) d/D-d. This form of lambda suggests that the dilute-to-dense transition is a global property of the flow, unlike the jamming transition which depends only on d/d(0). Furthermore, the transition is found to occur when the area fraction of particles near the exit exceeds a critical value which is close to 0.65+/-0.03.