Self-Similar Dynamics of Large Polymer Rings: A Neutron Spin Echo Study.

This work clarifies the self-similar dynamics of large polymer rings using pulsed-field gradient nuclear magnetic resonance and neutron spin echo spectroscopy. We find center of mass diffusion taking place in three dynamic regimes starting (i) with a strongly subdiffusive domain ⟨r^{2}(t)⟩_{com}∼t^{α} (0.4≤α≤0.65); (ii) a second subdiffusive region ⟨r^{2}(t)⟩_{com}∼t^{0.75} that (iii) finally crosses over to Fickian diffusion. While the t^{0.75} range previously has been found in simulations and was predicted by theory, we attribute the first to the effect of cooperative dynamics resulting from the correlation hole potential. The internal dynamics at scales below the elementary loop size is well described by ring Rouse motion. At larger scales the dynamics is self-similar and follows very well the predictions of the scaling models with preference for the self-consistent fractal loopy globule model.

Direct Assessment of Tube Dilation in Entangled Polymers.

A key ingredient within theories focusing on the rheology of entangled polymers is the way how the topological constraints of an entangled chain are lifted by unconstrained segments, i.e., how the constraining tube is dilated. This important question has been addressed by directly measuring the tube diameter d at the scale of the tube by neutron spin echo spectroscopy. The tube diameter d and plateau modulus G_{N}^{0} of highly entangled polyethylene oxide (PEO) chains of volume fraction c that are diluted by low molecular PEO show a concentration dependence d∝c^{a/2} and G_{N}^{0}∝c^{1+a} with an exponent a close to 4/3. This result allows the clear discrimination between different theoretical models that predict 4/3 or other values between 1 and 2 and provides an important ingredient to tube model theories.

Polymer Chain Conformation and Dynamical Confinement in a Model One-Component Nanocomposite.

We report a neutron-scattering investigation on the structure and dynamics of a single-component nanocomposite based on SiO_{2} particles that were grafted with polyisoprene chains at the entanglement limit. By skillful labeling, we access both the monomer density in the corona as well as the conformation of the grafted chains. While the corona profile follows a r^{-1} power law, the conformation of a grafted chain is identical to that of a chain in a reference melt, implying a high mutual penetration of the coronas from different particles. The brush crowding leads to topological confinement of the chain dynamics: (i) At local scales, the segmental dynamics is unchanged compared to the reference melt, while (ii) at the scale of the chain, the dynamics appears to be slowed down; (iii) by performing a mode analysis in terms of end-fixed Rouse chains, the slower dynamics is tracked to topological confinement within the cone spanned by the adjacent grafts; (iv) by adding 50% matrix chains, the topological confinement sensed by the grafted chain is lifted partially and the apparent chain motion is accelerated. We observe a crossover from pure Rouse motion at short times to topological confined motion beyond the time when the segmental mean squared displacement has reached the distance to the next graft.

Polymer dynamics under cylindrical confinement featuring a locally repulsive surface: A quasielastic neutron scattering study.

We investigated the effect of intermediate cylindrical confinement with locally repulsive walls on the segmental and entanglement dynamics of a polymer melt by quasielastic neutron scattering. As a reference, the corresponding polymer melt was measured under identical conditions. The locally repulsive confinement was realized by hydrophilic anodic alumina nanopores with a diameter of 20 nm. The end-to-end distance of the hydrophobic infiltrated polyethylene-alt-propylene was close to this diameter. In the case of hard wall repulsion with negligible local attraction, several simulations predicted an acceleration of segmental dynamics close to the wall. Other than in attractive or neutral systems, where the segmental dynamics is slowed down, we found that the segmental dynamics in the nanopores is identical to the local mobility in the bulk. Even under very careful scrutiny, we could not find any acceleration of the surface-near segmental motion. On the larger time scale, the neutron spin-echo experiment showed that the Rouse relaxation was not altered by confinement effects. Also the entanglement dynamics was not affected. Thus at moderate confinement conditions, facilitated by locally repulsive walls, the dynamics remains as in the bulk melt, a result that is not so clear from simulations.

Nanoscale Motion of Soft Nanoparticles in Unentangled and Entangled Polymer Matrices.

We have studied the motion of polyhedral oligomeric silsesquioxane (POSS) nanoparticles modified with poly(ethylene glycol) (PEG) arms immersed in PEG matrices of different molecular weight. Employing neutron spin echo spectroscopy in combination with pulsed field gradient (PFG) NMR we found the following. (i) For entangled matrices the center of mass mean square displacement (MSD) of the PEG-POSS particles is subdiffusive following a t^{0.56} power law. (ii) The diffusion coefficient as well as the crossover to Fickian diffusion is independent of the matrix molecular weight and takes place as soon as the center of mass has moved a distance corresponding to the particle radius-this holds also for unentangled hosts. (iii) For the entangled matrices Rubinstein's scaling theory is validated; however, the numbers indicate that beyond Rouse friction the entanglement constraints appear to strongly increase the effective friction even on the nanoparticle length scale imposing a caveat on the interpretation of microrheological experiments. (iv) The oligomer decorated PEG-POSS particles exhibit the dynamics of a Gaussian star with an internal viscosity that rises with an increase of the host molecular weight.

Molecular View on Supramolecular Chain and Association Dynamics.

The chain and association dynamics of supramolecular polymer ensembles decisively determines their properties. Using neutron spin echo (NSE) spectroscopy we present molecular insight into the space and time evolution of this dynamics. Studying a well characterized ensemble of linearly associating telechelic poly(ethylene glycol) melts carrying triple H-bonding end groups, we show that H-bond breaking significantly impacts the mode spectrum of the associates. The breaking affects the mode contributions and not the relaxation times as was assumed previously. NSE spectra directly reveal the so far intangible H-bond lifetimes in the supramolecular melt and demonstrate that for both the microscopic and the macroscopic dynamics of the supramolecular ensemble the instantaneous average of the M_{w} distribution governs the system response at least as long as the Rouse picture applies.

Manipulating the hydrophilic / hydrophobic balance in novel cationic surfactants by ethoxylation: The impact on adsorption and self-assembly.

HYPOTHESIS: Cationic surfactants have a wide range of applications, often associated with their affinity for a range of solid surfaces and their anti-microbial properties. Manipulating their adsorption and self-assembly properties is key to most applications, and this is commonly achieved through surfactant mixtures or manipulating their headgroup or alkyl chain structure. Achieving this through adjustments to their headgroup structure is less common in cationic surfactants than in anionic surfactants. Ethoxylation provides the ability to adjust the hydrophilic / hydrophobic balance, as extensively demonstrated in a range of anionic surfactants. EXPERIMENTS: This same approach has been applied here to a range of ethoxylated cationic surfactants in the form of the quaternary ammonium salts, and their tertiary nonionic equivalents before quaternisation. Their adsorption and self-assembly properties are investigated using predominantly the neutron scattering techniques of neutron reflectivity, NR, and small angle neutron scattering, SANS. FINDINGS: The trends in the adsorption at the air-water interface and the self-assembly in aqueous solution demonstrate how the hydrophilic / hydrophobic balance can be adjusted by varying the degree of ethoxylation and the alkyl chain length, and illustrate the degree of interdependence of the different structural changes. The variation in the adsorption and the micelle structure shows how the surfactant conformation / packing changes as the degree of ethoxylation and alkyl chain length increases and how the introduction of charge induces further changes.

Microscopic dynamics of polyethylene glycol chains interacting with silica nanoparticles.

We present high resolution neutron spectroscopic investigations of polyethylene glycol matrices interacting attractively with neat SiO2 nanoparticles. We observe a very rich dynamical picture that significantly contradicts earlier conclusions on such systems. Investigating a short chain matrix we realized that a fraction of chains is attached at the nanoparticle surface suppressing completely its translational diffusion. Nevertheless these attached chains undergo an unchanged segmental dynamics seemingly forming a micellelike corona of chains attached with their OH end groups. Changing to methyl-terminated chains the picture changes drastically, now showing a tightly adsorbed layer that however is not glassy as often assumed but undergoes fast picosecond local dynamics. With the singular importance of end groups, mean field approaches are not applicable and future simulations should be redirected to model such unexpected phenomena.

Direct observation of confined single chain dynamics by neutron scattering.

Neutron spin echo has revealed the single chain dynamic structure factor of entangled polymer chains confined in cylindrical nanopores with chain dimensions either much larger or smaller than the lateral pore sizes. In both situations, a slowing down of the dynamics with respect to the bulk behavior is only observed at intermediate times. The results at long times provide a direct microscopic measurement of the entanglement distance under confinement. They constitute the first experimental microscopic evidence of the dilution of the total entanglement density in a polymer melt under strong confinement, a phenomenon that so far was hypothesized on the basis of various macroscopic observations.

Liquid hydridosilane precursor prepared from cyclopentasilane via sonication at low temperatures without the action of light.

We report on a liquid hydridosilane precursor ink prepared via the ultrasonically induced ring-opening polymerisation of cyclopentasilane (Si5H10) without irradiation by ultraviolet light. The sonication is carried out in N2 atmosphere at temperatures between 20 and 75°C. We use size exclusion chromatography (SEC) to show polymer growth and estimate molecular mass with increasing sonication time. In combination with UV-vis transmission measurements, further SEC analysis is used to compare solutions subjected to either purely thermal or ultrasonic treatment at the same process temperature and for the same duration. Our findings provide strong evidence showing that the initiation of the polymerisation is sonocatalytic in nature and not thermic due to the macroscopic temperature of the solution. The liquid precursor is used to produce homogeneous hydrogenated amorphous silicon (a-Si:H) thin films via spin coating and pyrolytic conversion. The optoelectronic properties of the films are subsequently improved by hydrogen radical treatment. Fourier transform infrared spectroscopy (FTIR) is used to determine a compact film morphology and electrical conductivity measurements show that the layers attain a light-to-dark photosensitivity ratio of 2×103 making them suitable for application in optoelectronic devices.

Phase separation in star-polymer-colloid mixtures.

We examine the demixing transition in star-polymer-colloid mixtures for star arm numbers f=2,6,16,32 and different star-polymer-colloid size ratios 0.18< or =q< or =0.50. Theoretically, we solve the thermodynamically self-consistent Rogers-Young integral equations for binary mixtures using three effective pair potentials obtained from direct molecular computer simulations. The numerical results show a spinodal instability. The demixing binodals are approximately calculated and found to be consistent with experimental observations.

Advanced rheological characterization of soft colloidal model systems.

The complex flow behavior of polymer-based soft colloidal model systems was investigated using steady and oscillatory shear to prove new concepts for advanced rheological characterization. In the very dilute regime we investigated high molecular weight polybutadiene star polymers to quantify the internal relaxation time arising from the polymeric nature of these ultra-soft colloids. The observed shear-induced brush deformation is interpreted in terms of the internal Zimm time τ(z). The observed dependence of τ(z) on matrix viscosity can be explained by shrinkage of the star polymer due to an increasing incompatibility with increasing matrix molecular weight. The influence of the polymeric nature on the characteristic structural relaxation time in the concentrated regime was investigated using non-linear rheology following Wyss et al (SRFS) (2007 Phys. Rev. Lett. 98 238303). Here we used star-like block copolymer micelles to systematically tune the 'softness' of the colloids by variation of the block ratio. A master curve with proper scaling parameters could be generated independent of the degree of colloidal 'softness'. However, the obtained strain-rate independent structural relaxation time τ(0) was not observed in the linear regime. In addition, a high frequency discrepancy was clearly found in all our experimental data. Both reflect the shortcomings of the SRFS approach.

SANS study of polymer-linked droplets.

We report experimental results obtained from SANS on microemulsion droplets connected by a telechelic polymer. Thanks to its ability to anchor droplets through its short stickers, the addition of this polymer leads to the formation of transient aggregates. Measurements were performed on samples at low surfactant content in such a way that the droplets appear to be isolated with a separation distance longer than the end-to-end distance of the polymer. The locally spherical structure of the micelles is unchanged in size upon polymer addition whereas the large rise in scattered intensity at low Q is due to the induced effective attractive interaction between droplets. The fitting model that we propose allows a quantitative description of the bridging effect.

Hydrodynamic effects in bicontinuous microemulsions measured by inelastic neutron scattering.

The dynamical properties of bicontinuous microemulsions have been studied with neutron spin echo spectroscopy around length scales corresponding to the correlation peak q(0). Comparison of samples with different contrasts for neutrons shed light on the two modes dominated either by variation of the oil/water difference or surfactant concentration in the hydrodynamic regime. The results have been compared to theoretical predictions of the relaxation rates of bicontinuous microemulsions by Nonomura and Ohta [M. Nonomura, T. Ohta, J. Chem. Phys. 110, 7516 (1999)]. The influence of modification of the surfactant layer bending constants in the microemulsion by addition of homopolymers (polyethylenepropylene: PEP(X) and polyethyleneoxide: PEO(X), X=5 kg/mol), dissolved in the oil phase and water, has been investigated.

An in situ study of the t-butyllithium initiated polymerization of butadiene in d-heptane via small angle neutron scattering and 1H-NMR.

We present a combined 1H-NMR and small angle neutron scattering in situ study of the anionic polymerization of butadiene using t-butyllithium as the initiator. Both initiation and propagation phases were explored. This combined approach allows the structural and kinetic characteristics to be accessed and cross compared. The use of the D22 instrument (ILL Grenoble) permits the attainment of Q approximately equal to 2 x 10(-3) A. This, in turn, led to the identification of coexisting large-scale and smaller aggregates during all stages of the polymerization. The smaller aggregates contain most of the reacted monomers. Their structure changes from high functionality wormlike chains at early stages of the reaction to starlike aggregates where the crossover occurs at a degree of polymerization of approximately equal to 40. The initiation event involved these small, high functionality (approximately equal to 120) aggregates that apparently consisted of cross-associated t-butyllithium with the newly formed allylic-lithium head groups. As the initiation event progressed the initiation rate increased while the functionality of these small aggregates decreased and their size increased. Propagation, in the absence of initiation, was found to have a rate constant that was molecular weight dependent. At approximately 11 kg/mol the measured polymerization rate was found to increase while no further structural changes were seen.

Microemulsion efficiency boosting and the complementary effect. 1. Structural properties.

Amphiphilic diblock copolymers added to microemulsions proved to enhance the efficiency of surfactants dramatically. The complementary effect of homopolymers is considered in the current work. A possible application of the homopolymer addition could be the viscosity tuning of the microemulsion without changing the considered bicontinuous phase. Furthermore, (homo)polymers are added for many other reasons in technical applications. A theory by Eisenriegler predicts a decreased efficiency when homopolymers are added. In further experiments, the simultaneous addition of homopolymers and diblock copolymers probes whether the two opposite effects superpose and allow for a compensation. Then, efficiency and viscosity are adjustable independently. Experimentally, phase diagrams are investigated and the microscopic structure is measured by small-angle neutron scattering. Within the presented models, both experimental methods are compared and discussed on the basis of the surfactant membrane bending moduli. The homopolymer effect is about 7 times larger than that theoretically predicted, and the superposition of the two polymer effects allows for a compensation with an optionally tunable viscosity.

Membrane decoration by amphiphilic block copolymers in bicontinuous microemulsions.

The effect of various amphiphilic block copolymers of different molar masses on the structure and phase behavior of ternary amphiphilic systems (water, oil, and nonionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic increase in the volumes of oil and water, which can be solubilized in a bicontinuous microemulsion. High-precision neutron scattering experiments with a sophisticated contrast variation technique demonstrate that the polymers form uniformly distributed mushroom conformations on the surfactant membrane. Based on these observations, we propose a universal mechanism for the swelling behavior, which is due to the variation of the membrane curvature elasticity.