Small-angle X-ray scattering from salt-free solutions of star-branched polyelectrolytes

The dispersion state of sodium-sulphonated polystyrene ( NaPSS) star-branched polyelectrolytes was investigated in salt-free aqueous solutions, by use of the small-angle X-ray scattering technique. With respect to polystyrene (PS) star-branched polymers of identical functionality, the ordering phenomenon occurring in the neighborhood of the overlap concentration c^* is reinforced and observed in a larger range of concentrations. Moreover, the degree of order is no longer maximum at c^* and is improved as the concentration decreases. The dispersion state is then mainly controlled by the electrostatic interaction. A crystalline order should therefore be achieved with stars of lower functionality, provided the electrostatic interaction is added to the osmotic repulsion. On the other hand, unusual scattering patterns are measured for aqueous solutions of NaPSS star polyelectrolytes. Indeed, a diffuse scattering is revealed at high angles, in addition to the regular diffraction rings related to preferred interstar distances. It is similar to the broad scattering peak produced by semidilute solutions of NaPSS linear polyelectrolytes and associated to the electrostatic correlation hole within the isotropic model. In the dilute regime (c < c ^*), it is just an intramolecular characteristic and represents the electrostatic repulsion between arms belonging to the same star. In the semidilute regime (c > c ^*), it also reflects the electrostatic repulsion between arms of distinct stars. So, as the concentration increases, it is mainly caused by the interpenetration of NaPSS stars. Such an observation is in agreement with the composite structure earlier proposed by Daoud and Cotton for star semidilute solutions. For c > c ^*, NaPSS star aqueous solutions can therefore be pictured as effective stars immersed in a matrix formed by the overlap of the arm ends. With respect to the dilute regime, the effective stars are smaller; the higher the concentration the smaller the size. Received 14 May 1999 and Received in final form 15 March 2000     

Structural and dynamical properties of aqueous suspensions of NaPSS (HPSS) at very low ionic strength

Results on the structural and dynamical properties of aqueous solutions of NaPSS (HPSS) are reported. Most samples of previous measurements, including our own, are contaminated by the presence of (temporal) aggregates. The emphasis of this paper lies on investigations of well purified samples at very low ionic strength where interacting effects are maximum. As previously reported, this can be achieved by pumping the suspension through ion exchange resin by means of a tube-pump, using filters of pore size. Information has been extracted from static and dynamic light scattering and viscosity measurements. A second maximum is observed in the scattering curves versus wavenumber for the first time. It is discussed on the basis of two current models describing the structure of charged macromolecules. The short time dynamics reflects the measured intensity. Detailed viscosity data in comparison of those of rodlike (TMV), slightly flexible so-called fd virus particles (length 880 nm) are used to confirm the interpretation of the light scattering results. The recently observed maximum in the reduced viscosity could be confirmed. Received: 5 May 1997 / Revised: 1 September 1997 / Accepted: 10 November 1997     

Electric field light scattering by flexible linear polyelectrolytes in aqueous solution

Electric field light scattering results on aqueous solutions of linear, flexible NaPSS at minimal ionic strength are reported. Samples of molecular weights between 356 kg/mol and 2870 kg/mol were investigated. With increasing field strength the intensity as a function of wavenumber develops a pronounced oscillating behaviour. Besides the well-known first peak a second maximum is observed at the position at which a weak maximum for some samples already occurs at zero field. The overall intensity strongly depends on the frequency of the electric field. The electro-optical effect shows a maximum at 300 kHz. Increasing the particle concentration gives a large increase of the peak maximum, normalized to concentration. If plotted versus scattering angle the relative intensity increase is maximum for samples of medium molecular weight. The results strongly indicate a stretching and alignment of the chains, thus leading to or enlarging the short range order of the chains. Received 9 April 1999 and Received in final form 18 August 1999     

Molecular-dynamics simulation of a glassy polymer melt: Incoherent scattering function

We present simulation results for a model polymer melt, consisting of short, nonentangled chains, in the supercooled state. The analysis focuses on the monomer dynamics, which is monitored by the incoherent intermediate scattering function. The scattering function is recorded over six decades in time and for many different wave-vectors which range from the size of a chain to about three times the maximum position of the static structure factor. The lowest temperatures studied are slightly above , the critical temperature of mode-coupling theory (MCT), where was determined from a quantitative analysis of the - and -relaxations. We find evidence for the space-time factorization theorem in the -relaxation regime, and for the time-temperature superposition principle in the -regime, if the temperature is not too close to . The wave-vector (q-) dependence of the nonergodicity parameter, of the critical amplitude, and the -relaxation time are in qualitative agreement with calculations for hard spheres. For q larger than the maximum of the structure factor the -relaxation time already agrees fairly well with the asymptotic MCT-prediction . The behavior of the relaxation time at small q can be rationalized by the validity of the Gaussian approximation and the value of the Kohlrausch stretching exponent, as suggested in neutron-scattering experiments. Received 30 October 1998     

Characterization of the structure and the size distribution of branched polymers formed by co-polymerization of MMA and EGDMA

Free radical co-polymerization of methyl methacrylate (MMA) and ethyl glycol dimethyl methacrylate (EGDMA) in solution leads to the formation of polydisperse branched PMMA which grows in size until the system gels. The structure and the size distribution of the PMMA aggregates were characterized at infinite dilution using static and dynamic light scattering and size exclusion chromatography (SEC). The reaction extent was measured using SEC and Raman spectroscopy. The results show that the structure and size distribution of PMMA aggregates formed close to the gel point are compatible with those of percolating clusters. The structure factor of semi-dilute solutions of PMMA aggregates is the same as that of dilute solutions at distance scales much smaller than the correlation length of the concentration fluctuations (). However, the cut-off function of the pair correlation function at for semi-dilute solutions is more gradual than the cut-off function at for dilute solutions. Received 11 May 1998 and Received in final form 22 October 1998     

Structural evidence of charge renormalization in semi-dilute solutions of highly charged polyelectrolytes

We show experimentally that Manning counterion condensation also leads to a renormalization of the charge density at high concentrations of highly charged, flexible, hydrophilic polyelectrolytes. Investigations by small angle neutron and X-ray scattering of semi-dilute solutions of poly(acrylamide-co-sodium-2-acrylamido-2-methylpropane sulfonate) at different charge densities above the condensation threshold, show that the scattering function is invariant with the charge density. Received 16 June 1998     

Dynamic and static light scattering study of the formation of cross-linked PMMA gels

Free radical co-polymerization of methyl methacrylate (MMA) and ethyl glycol dimethyl metacrylate (EGDMA) was investigated in solution at different molar ratios R = [EGDMA]/[MMA] between 0 and 0.05. Initially mainly linear PMMA was formed with weight average molar mass 7.5 g/mol independent of R. At larger reaction extents branched polymers were formed and the systems gelled. The scattering intensity rose initially with the reaction extent, but reached a plateau value at larger reaction extents. The plateau value increased strongly with R. Dynamic light scattering showed the appearance of a slow relaxation not observed in linear PMMA solutions. The data can be interpreted by assuming that the excess scattering originates from the branching points and relaxes through self diffusion of the branched particles. The results agree with predictions of the percolation model for gelation and Rouse dynamics. Viscosity measurements corroborate this interpretation. Measurements on a progressively diluted sample quenched close to the gel point again showed quantitative agreement with the percolation model for gelation. Received 11 May 1998 and Received in final form 22 October 1998     

The state space of short-range Ising spin glasses: the density of states

The correlations between the segments of a semidilute polymer solution are found to induce correlations in the positions of small particles added to the solution. Small means a diameter much less than the polymer's correlation length. In the presence of polymer the particles behave as if they attracted each other. It is shown how the polymer's correlation length may be determined from a scattering experiment performed on the spheres. Received: 7 July 1997 / Received in final form: 12 November 1997 / Accepted: 19 November 1997     

Swelling behavior and viscoelasticity of ultrathin grafted hyaluronic acid films

In this paper we study the effect of monovalent and divalent ions on the swelling behavior and viscoelastic parameters of ultrathin layers of the natural polyelectrolyte hyaluronic acid covalently coupled to glass substrates. A colloidal probe technique is applied for this purpose based on latex beads, hovering over the polymer cushion. By analyzing the vertical Brownian motion of these beads with reflection interference contrast microscopy (RICM) we determined the equilibrium layer thickness (with 3 nm vertical resolution), the interfacial interaction potential, and the characteristic mesh size limiting the hydrodynamic flow within the polyelectrolyte film as a function of the ionic strength. The experimental results are interpreted in terms of three different theoretical models: the polyelectrolyte brush approximation of Pincus [#!ref1!#], a modified polyelectrolyte brush approximation in the high salt concentration limit of Ross and Pincus [#!ref2!#] and the simple scaling approximation for neutral adsorbed polymers of de Gennes [#!ref3!#]. Within experimental error all of these different models fit our experimental data and yield comparable results for the equilibrium layer thickness. Moreover we determine a thickness dependent, effective surface coverage from both brush models. The hydrodynamic properties of the films are interpreted in terms of the Brinkmann model of elastic porous media by assuming an effective mesh size, which depends linearly on the Debye screening length. The salt induced condensation of the polyelectrolyte films can be described microscopically in terms of a progressive contraction of the mesh size with increasing salt concentration. Received 10 September 1998 and Received in final form 30 November 1998     

Compression of a soft sphere packing

Mechanical properties of packings of deformable spheres of polyelectrolyte gel are studied experimentally. These particles are plunged into a brine. They have the property to swell and shrink when the concentration of salt of the solution is varied. An oedometric compression is performed imposing cycles of deformation at constant speed and constant salinity C_s. Under many different conditions, we study the laws of deformation relating the macroscopic compression force F, to the macroscopic strain . We find empirical non linear relations of the type . The values of this exponent m are discussed and compared to the results of measurements on a single sphere compressed on a plane as well as to the results of experiments and simulations on dry model granular assemblies. The swelling and deswelling properties of the spheres are used to perform isotropic compression tests. In this situation we determine the relation between the force at equilibrium and the macroscopic strain . The results are compared with those obtained in the oedometric compression tests. Received 27 January 1998     

Compression induced phase transitions in PEO brushes: the n-cluster model

The compression of brushes of terminally anchored chain within the de Gennes n-cluster model is analysed. This model was developed for Poly(ethylene oxide) in water but may apply to other systems. Brushes described by this model exhibit discontinuous concentration profile associated with the coexistence of an inner dense “phase” and an outer, dilute, one. The compression induces growth of the dense, weakly compressible region. This, in turn, gives rise to distinctive force profiles associated with changes of slope. When the dilute region disappears, the compression of two brushes can give rise to a transient attraction. Received: 4 November 1997 / Revised: 29 January 1998 / Accepted: 24 March 1998     

Identification of flow mechanisms for a soft crystal

We study the behavior under flow of soft spherical micelles forming a fcc phase at high volume fraction. Due to the size (300 ?) of the elementary objects, the structure can be investigated through X-rays and neutron scattering, at rest and under flow in a Couette cell. Using scattering in two perpendicular directions, different mechanisms of flow are identified. At intermediate shear (around 100 s^-1) the system exhibits the so called layer sliding mechanism where two dimensional hexagonal compact planes of spheres align themselves with the Couette cell walls. At lower shear rate, the fcc structure is locally preserved, and the flow is mediated by defects between crystallites. At high shear rate, we observe the melting of the structure and a liquid-like structure factor. Moreover, we were able to use the existence of the layer sliding regime to generate a fcc monocrystal by annealing the satcking faults between the decorrelated planes created by the layer sliding. Received: 7 July 1997 / Received in final form: 16 January 1998 / Accepted: 5 March 1998     

Scattering properties of salt-free wormlike micellar solutions

Static and dynamic light scattering and conductivity experiments were carried out on salt-free aqueous micellar solutions of cetyltrimethylammonium n-hexane sulfonate (CTAC_6SO_3) and cetyltrimethylammonium n-heptane sulfonate (CTAC_7SO_3) as a function of surfactant concentration. This study confirms the analogy between the behavior in the semi-dilute regime of elongated micellar systems and “classical” polyelectrolyte solutions. Time-resolved scattering experiments performed after a variation of concentration from about twice the overlap volume fraction to less than half of it revealed the existence of a structural relaxation with a characteristic time of several hours. Received 21 December 1999     

Viscosity at small scales in polymer melts

Flows around small colloidal particles of diameter b, or in thin films, capillaries, etc., cannot always be described in terms of the macroscopic polymer viscosity. We discuss these features for entangled polymer melts, where two distinct regimes can be found: (a) the thin regime where b is smaller than the coil radius R₀, but larger than the diameter of the Edwards tube; (b) the ultrathin regime, where . We consider (i) non adsorbing particles, where slippage may occur between the melt and the solid surface; (ii) “hairy” particles, which carry some bound polymer chains. We obtain scaling predictions for mobilities of spheres, of needles, and of clusters of particles. We also discuss translational and rotational diffusion of needles. Received 19 April 1999     

Self-organized criticality on quasiperiodic graphs

It is shown that quasielastic scattering of ultracold neutrons due to diffusive motion of scatterers at the surface of liquid polymer (fomblin) or adsorbed hydrogenous contaminations of the surface of neutron traps may be possible reason of their energy spreading during long storage time in closed traps, which was observed in the recent experiments. Received 8 July 1998     

Chord length distributions and small-angle scattering

Chord length distributions describe size, shape and spatial arrangement of geometrical objects (particles). The chord length distribution is in principle proportional to the second derivative of the correlation function of small-angle scattering. It is calculable from a relative measurement of the scattering intensity I(h). In structure research, the characterization of numerous particle systems can be achieved by comparing experimental chord distributions with theoretical ones, provided the latter are available with sufficiently high precision for a lot of fundamental, universal shapes. Both sides of this concept are exemplified: – the step from a relative measurement of the scattering intensity of an isotropic two-phase sample to the chord length distribution (errors in and in , limited h-interval, corresponding to the region (1-2) nm < r in real space, must be observed); as well as the geometric matter of calculation of chord distributions as fingerprints for basic geometric figures, including the non-convex case. Received 15 March 1999 and Received in final form 26 April 2000     

Nematic ordering in anisotropic elastomers: Effect of frozen anisotropy

Nematic ordering in anisotropic non-Gaussian elastomers is considered theoretically using mean field approximation. We focus on the effect of anisotropy during network cross-linking on the system elasticity and, in particular, on the so-called soft deformation mode. As the main result, we calculate the dependence of the elastomer free energy on the angle between the axis of “frozen” anisotropy and the nematic director. The dependence of the isotropic-nematic transition point on the orientational field acting on the monomers during the cross-linking process is also calculated. Received: 5 November 1997 / Revised and Accepted: 29 June 1998     

Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

Structural properties of charged diblock copolymer solutions

Aqueous micellar solutions of ionic/neutral block copolymers have been studied by light scattering, small angle neutron scattering and small angle X-ray scattering. We made use of a polymer comprised of a short hydrophobic block (polyethylene-propylene) PEP and of a long polyelectrolytic block (polystyrene-sulfonate) PSSNa which has been shown previously to micellize in water. The apparent polydispersity of these micelles is studied in detail, showing the existence of a few large aggregates coexisting with the population of micelles. Solutions of micelles are found to order above some threshold in polymer concentration. The order is liquid-like, as demonstrated by the evolution with concentration of the peak observed in the structure factor (), and the degree of order is found to be identical over a large range of concentrations (up to 20 wt%). Consistent values of the aggregation number of the micelles are found by independent methods. The effect of salt addition on the order is found to be weak. Received: 19 June 1997 / Received in final form: 4 September 1997 / Accepted: 9 October 1997