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     

Ordering of urchin-like charged copolymer micelles: Electrostatic, packing and polyelectrolyte correlations

We report the results of small-angle neutron scattering (SANS) studies on aqueous solutions of spherical polyelectrolyte micelles formed by association of charged-neutral diblock copolymers. The neutral moieties are found to self-assemble into small dense spheres (cores of the micelles) whose sizes are independent of the polymer concentration c. In the dilute regime, c<c ^*, where c^* is the overlap concentration of the micelles, the conformation of the charged groups, which form the corona of the micelles, is found to be extended. A liquid-like order is observed over a wide concentration range spanning from the dilute regime to the concentrated regime. For c>c ^*, polyelectrolyte correlations appear at smaller spatial scales and coexist with the liquid-like order. These results suggest that for dense brushes, above c^*, the rod-like statistics of the charged chains begin to disappear due to contraction of corona arms or by interpenetration of coronae. For less dense brushes, the charged chains are found to be extended up to concentrations far above c^*, before the progressive development of polyelectrolyte correlations. Received 8 October 1999     

A FT-IR absorption analysis of vibrational properties of water encaged in NaA zeolites: evidence of a “structure maker” role of zeolitic surface

Linear polyisoprenes having dimethylamine end groups were prepared by high vacuum anionic polymerization techniques using 3-dimethylaminopropyllithium as the initiator. The amine group was reacted with 2-cholesteryl-2-oxo-1,3,2-dioxaphospholane to provide polymer chains having end zwitterionic groups chemically connected with cholesterol. The association behavior of these end-functionalized polymers was studied in cyclohexane by low angle laser light scattering, dynamic light scattering, and viscometry. The aggregation numbers, N _w were found to decrease by increasing the molecular weight of the precursor polymer, due to excluded volume repulsions. The ability of cholesterol to form liquid crystal mesophases facilitated the association process leading to higher N _w values. The hydrodynamic behavior of the aggregates was similar to that of star polymers. The dependence of the N _w values on the molecular weight of the base polymer, the polydispersity of the associates and the absence of critical micelle concentration, cmc are compatible with the linear head-packing model. Received 29 April 2002 and Received in final form 13 November 2002 Published online: 11 March 2003     

Phase behavior of a suspension of hard spherocylinders plus ideal polymer chains

We study isotropic-isotropic and isotropic-nematic phase transitions of fluid mixtures containing hard spherocylinders (HSC) and added non-adsorbing ideal polymer chains using scaled particle theory (SPT). First, we investigate isotropic-nematic (I -N phase coexistence using SPT in the absence of polymer. We compare the results obtained using a Gaussian form of the orientational distribution function (ODF) to minimize the free energy versus minimizing numerically. We find that formal numerical minimization gives results that are much closer to computer simulation results. In order to describe mixtures of HSC plus ideal chains we studied the depletion of ideal chains around a HSC. We analyze the density profiles of ideal chains near a hard cylinder and find the depletion thickness δ is a function of the ratio of the polymer's radius of gyration R_g and the cylinder radius R_c. Our results are compared with a common approximation in which the depletion thickness is taken equal to the radius of gyration of the polymer chain. We incorporate the correct depletion thickness into SPT and find that for R _g/R _c < 1.56 using ideal chains gives phase transitions at smaller polymer concentrations, whereas for R _g/R _c > 1.56 , which is a common experimental situation, the phase transitions are found at larger polymer concentrations with respect to δ = R _g . The differences are significant, especially for R _g ≫ R _c , so we can conclude it is essential to take into account the properties of ideal polymer chains and the resulting depletion near a cylinder. Finally, we present phase diagrams for rod-polymer mixtures which could be realized under experimental conditions.     

Phase behaviour of a dispersion of charge-stabilised colloidal spheres with added non-adsorbing interacting polymer chains

We present a theory for the phase behaviour of mixtures of charge-stabilised colloidal spheres plus interacting polymer chains in good and θ -solvents within the framework of free-volume theory. We use simple but accurate combination rules for the depletion thickness around a colloidal particle and for the osmotic pressure up to the semi-dilute concentration regime. Hence, we obtain expressions for the free energy for mixtures of charged colloidal particles and non-adsorbing interacting polymers. From that, we calculate the phase behaviour, and discuss its topology in dependence on the competition between the charge-induced repulsion and the polymer-induced attraction. The homogeneous mixture of colloids and polymers becomes more stabilised against demixing when increasing the electrostatic repulsion. This charge-induced stabilisation is strongest for small polymer-to-colloid size ratios and is more pronounced for charged colloids mixed with polymers in a good solvent than for polymers in a θ -solvent. For the weakly charged regime we find that the phase diagram becomes salt-concentration-independent in the protein limit for charged colloids plus polymers in a θ -solvent. The liquid window, i.e., the concentration regimes where a colloidal liquid exists, is narrowed down upon increasing the charge-induced repulsion. Also this effect is more pronounced when charged colloids are mixed with polymer chains in a good solvent. In summary, we demonstrate that the solvent quality significantly influences the phase behaviour of mixtures of charged colloids plus non-adsorbing polymers if the range of the screened electrostatic repulsion becomes of the order of the range of the depletion-induced attraction.     

线性高分子体系中高分子链间排除体积效应的模型化

提出了线性高分子体系中高分子链间排除体积效应的一个它回避模型，并且针对具体的四个模型系统进行了计算机模拟. 计算结果表明：1)线团的均方末端距〈R²〉与行走步数(N)仍然保持着与无规线团模型一样的线性关系；2)但与无规线团相比，线团的空间尺寸被压缩；3)与两侧方向的回避相比，在行走的前进方向的回避而导致的压缩效应更加明显. 关键词： 排除体积效应 回避行走 无规线团 线性高分子     

Phase behaviour of colloid-polymer mixtures

Summary We review the phase behaviour of mixtures of colloids and non-adsorbing polymers. The exclusion of polymer molecules from overlapping ?depletion zones? between two neighbouring colloidal particles results in an unbalanced osmotic pressure pushing the particles together. This depletion potential is separately tunable in range and depth. Theory predicts that the resulting phase behaviour is sensitive to ξ=r _g/R, the ratio of the radius of gyration of a polymer molecule, to the radius of the colloid. At large ξ, a stable colloidalliquid phase becomes possible. This has been confirmed by recent experiments. The formation of non-equilibrium ?transient gel? states when the size ratio is small (≈0.08) is also introduced briefly. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Phase behaviour of polyethylene knotted ring chains

The phase behaviour of polyethylene knotted ring chains is investigated by using molecular dynamics simulations. In this paper, we focus on the collapse of the polyethylene knotted ring chain, and also present the results of linear and ring chains for comparison. At high temperatures, a fully extensive knot structure is observed. The mean-square radius of gyration per bond ² / (Nb²) and the shape factor <δ^*> depend on not only the chain length but also the knot type. With temperature decreasing, chain collapse is observed, and the collapse temperature decreases with the chain length increasing. The actual collapse transition can be determined by the specific heat capacity C_v, and the knotted ring chain undergoes gas-liquid-solid-like transition directly. The phase transition of a knotted ring chain is only one-stage collapse, which is different from the polyethylene linear and ring chains. This investigation can provide some insights into the statistical properties of knotted polymer chains.     

Scattering from solutions of star polymers

We study the scattering intensity of dilute and semi-dilute solutions of star polymers. The star conformation is described by a model introduced by Daoud and Cotton. In this model, a single star is regarded as a spherical region of a semi-dilute polymer solution with a local, position dependent screening length. For high enough concentrations, the outer sections of the arms overlap and build a semi-dilute solution (a sea of blobs) where the inner parts of the actual stars are embedded. The scattering function is evaluated following a method introduced by Auvray and de Gennes. In the dilute regime there are three regions in the scattering function: the Guinier region (low wave vectors, ) from where the radius of the star can be extracted; the intermediate region () that carries the signature of the form factor of a star with f arms: ; and a high wavevector zone () where the local swollen structure of the polymers gives rise to the usual q ^-5/3 decay. In the semi-dilute regime the different stars interact strongly, and the scattered intensity acquires two new features: a liquid peak that develops at a reciprocal position corresponding to the star-star distances; and a new large wavevector contribution of the form q ^-5/3 originating from the sea of blobs. Received: 3 September 1997 / Revised: 13 January 1988 / Accepted: 31 March 1998     

Monte Carlo studies of two measures of polymer chain size as a function of temperature

Monte Carlo simulations of single polymer chains with both excluded volume and nearest-neighbor interaction energies are discussed. Two measures of chain size are obtained in the simulation, the radius of gyration of the polymer chain and the inverse radius of the polymer chain. Both of these are reported as a function of temperature, or interaction energy, and chain length,N. The possibility of estimating the fractal dimensions of these measures from the Monte Carlo data is discussed in the context of two different interpolation functions for the temperature dependence of the fractal dimensions. The approach to the fractal dimension as a function of chain length,N, is studied. It is suggested that the approach to fractal dimension of the measures of chain size of polymers is slow, perhaps a fractional power itself.     

Investigation of Ring and Star Polymers in Confined Geometries: Theory and Simulations

The calculations of the dimensionless layer monomer density profiles for a dilute solution of phantom ideal ring polymer chains and star polymers with f=4 arms in a Θ -solvent confined in a slit geometry of two parallel walls with repulsive surfaces and for the mixed case of one repulsive and the other inert surface were performed. Furthermore, taking into account the Derjaguin approximation, the dimensionless layer monomer density profiles for phantom ideal ring polymer chains and star polymers immersed in a solution of big colloidal particles with different adsorbing or repelling properties with respect to polymers were calculated. The density-force relation for the above-mentioned cases was analyzed, and the universal amplitude ratio B was obtained. Taking into account the small sphere expansion allowed obtaining the monomer density profiles for a dilute solution of phantom ideal ring polymers immersed in a solution of small spherical particles, or nano-particles of finite size, which are much smaller than the polymer size and the other characteristic mesoscopic length of the system. We performed molecular dynamics simulations of a dilute solution of linear, ring, and star-shaped polymers with N=300 , 300 (360), and 1201 (4 × 300 + 1-star polymer with four arms) beads accordingly. The obtained analytical and numerical results for phantom ring and star polymers are compared with the results for linear polymer chains in confined geometries.     

Vortex pinning in YBa2Cu3O7?x films

Evidence that pinning on linear or planar defects dominates the vortex dynamics in YBa₂Cu₃O_7−x (YBCO) films is provided by complex impedance measurements at temperature 8 K<T<T _c and magnetic field 0<B<6 T. Below the vortex lattice melting transition B_g(T) but above a threshold field B_p≈8(1-T/T _c ) T, the inductance of vortices increases as B², much less rapidly than predicted for collective pinning of vortices by point defects. Above the vortex melting line, critical scaling persists over the region B_g(T<B<B^*(T) where the vortex correlation length ξ exceeds a characteristic length scale ξ^*≡ξ(B=B^*)≈450?. The value of ξ^* is not sensitive to Al-doping in the Cu sites in the lattice and is close to the size of twin domains in the film. The nature of the observed crossovers is discussed in terms of available theoretical models for a glass-liquid transition at B_g.     

Exact quantum partition function of the BCS model

The exact calculation of the reduced BCS model quantum partition function (QPF) in the thermodynamic limit is carried out by the path integration method. The expression for the QPF and the phase transition temperatureT _c in the regular phase coincide with the results of Bogolyubov. In the nonregular phase a temperature singularity appears in the expression for the QPF: the QPF diverges in the region of temperaturesT _c which are smaller than some critical temperatureT _c ^* , and it turns out that in all casesT _c ^* > T _c and the differenceT _c ^* –T _c is not small. The interpretation of the temperatureT _c ^* is given.     

Porous piezoelectric composites with extremely high reception parameters

The reception parameters Q ₃₃ ^* and Q _h ^* of modified fiber composites based on high-e ₃₃ ^FC /c ₃₃ ^{FC, E} ferroelectric piezoceramics (e ₃₃ ^FC is the piezoelectric constant, c ₃₃ ^{FC, E} is the elastic modulus) are considered as functions of the electromechanical properties and the porosity of the components. Pore configurations at which the values (Q ₃₃ ^* )²≈(Q _h ^* )²≈7×10⁻⁹ Pa⁻¹ for the polymer matrices of 1-0-3 composites are much higher than for conventional ternary composites are analyzed.     

Pressure-volume-temperature relations of a poly-ε-caprolactam and its nanocomposite

The equation of state of a poly-ε-caprolactam melt, PA-6, of molar mass M _n = 22 kg/mol was investigated in a Gnomix apparatus (Gnomix Inc., Boulder, Colorado) between 300 and 560 K, and pressures up to 150 MPa. Corresponding measurements were performed with addition of 1.6 wt% of montmorillonite exfoliated particles. Reductions in specific volume of about 1.0 and 1.4%, respectively, at 10 and 150 MPa, are observed. For the melt, excellent agreement between experiment and the results from lattice-hole theory is found for both systems. Addition of the nanoparticles reduced the hole (free volume) fraction by 14%. Evidently, the hole fraction is a sensitive indicator of structural changes. It is noteworthy that such a small quantity of added nanoparticles increases the tensile strength by about 14% and modulus by 26%, at a cost of reduction in the elongation at break by about 25%. For a treatment of the PNC, and as an approximation, our earlier model of a particulate composite was adopted. To calculate the binary interaction parameters it was assumed that: (1) the clay particles are in form of flat disks, 100 nm diameter and 1 nm thick; (2) the hard core segments of polymer and of solid occupy the same lattice volume, i.e. v ^* ₁₁ = v ^* ₂₂; (3) the energetic interactions of polymer with solid are given by the geometric average between the two self-interactions. These assumptions lead to the following results ('11' represents polymer-polymer, '22' represents clay-clay and '12' represents polymer-clay interactions): ε ^* ₁₁= 32.09; ε ^* ₁₂ = 313.54 and ε ^* ₂₂ = 3063 (kJ/mol) v ^* ₁₁ = 24.89; v ^* ₁₂ = 33.53 andv ^* ₂₂ = 24.89 (ml/mol)     

Invariance quantum group of the fermionic oscillator

The fermionic oscillator defined by the algebraic relations cc ^* +c ^* c = 1 and c ² = 0 admits the homogeneous group O(2) as its invariance group. We show that the structure of the inhomogeneus invariance group of this oscillator is a quantum group. Received: 15 July 2002 / Revised version: 14 October 2002 / Published online: 19 February 2003     

The elastic behaviour of ferroelastic Sb5O7I polytype 2MC studied by ultrasonic experiments and Brillouin scattering

The temperature dependence of the elastic functions of the improper ferroelastic polytype 2MC-Sb₅O₇I has been investigated in the temperature range from room temperature to well above the structural phase transition atT _c=481 K. The stiffnessesc(c^*c^*),c(a,a),c ₂₂ andc(c^*a) show a considerable softening up to 20% aroundT _c whereasc ₄₄ remains unaffected by the phase transition. The experimental results are discussed considering cubic and quartic anharmonic coupling between two components of the zone boundary order parameter and elastic waves.Carried out in Laboratories RCA Ltd, Zürich, SwitzerlandCarried out in Fakultät für Physik der Universität, Regensburg, Federal Republic of Germany     

The “corset effect” of spin-lattice relaxation in polymer melts confined in nanoporous media

Linear polyethylene oxides with molecular weightsM _w of 1665 and 10170 confined in pores with variable diameters in a solid methacrylate matrix were studied by proton field-cycling nuclear magnetic resonance relaxometry. The pore diameter was varied in the range of 9–57 nm. In all cases, the spin-lattice relaxation time shows a frequency dependence close toT ₁∞ v^3/4 in the range ofv=3·10^?1-2·10¹ MHz as predicted by the tube-reptation model. This protonT ₁ dispersion essentially reproduces that found in a previous deuteron study (R. Kimmich, R.-O. Seitter, U. Beginn, M. Möller, N. Fatkullin: Chem. Phys. Lett. 307, 147, 1999). As a feature particularly characteristic for reptation, this finding suggests that reptation is the dominating chain dynamics mechanism under pore confinement in the corresponding time range. The absolute values of the spin-lattice relaxation times indicate that the diameter of the effective tubes in which reptation occurs is much smaller than the pore diameters on the time scale of spin-lattice relaxation experimens. An estimation leads to a valued ^*～0.5 nm. The impenetrability of the solid pore walls, the uncrossability of polymer chains (“excluded volume”) and the low value of the compressibility in polymer melts create the “corset effect” which reduces the lateral motions of polymer chains to a microscopic scale of only a few tenths of a nanometer.     

Stratification of foam films made from polyelectrolyte solutions

Studies of thin liquid films, made from semidilute polyelectrolyte solutions, are presented. The disjoining pressure variation with film thickness exhibits oscillations, corresponding to film stratification. The oscillations become sharper as the polymer concentration c increases, and disappear when salt is added. The period of the oscillations scales as c ^-1/2. The observed stratification is related to the polymer network and the size of the steps to the mesh size ξ. Received 25 April 2000 and Received in final form 3 October 2000