E. Yu. Kramarenko

Molecular dynamics simulation study of adsorption of polymer chains with variable degree of rigidity. I. Static properties

The adsorption of a single polymer chain onto a solid surface is investigated by molecular dynamics simulations. The chain is composed of mass points interacting via a truncated Lennard‐Jones potential, i.e., the excluded volume interaction is taken into account, and grafted to the surface with one end. The average adsorption degree is calculated for various chain lengths (N = 16, 32, 64, 128) and adsorption energies. In addition, the scaling behavior of the adsorption degree and the radius of gyration is investigated. The adsorption degree and the average length of loops and tails are obtained for chains of various stiffnesses. In this context, we find that stiffer chains adsorb more easily. Moreover, the distribution of the mass points perpendicular to the surface as well as the orientation of the bonds with respect to the surface is discussed for various adsorption energies and stiffnesses.

Effect of a homogeneous magnetic field on the mechanical behavior of soft magnetic elastomers under compression

The mechanical properties of new magnetic composite materials were studied. The above materials represent rubbery silicon matrices filled with magnetic microparticles of metallic iron or magnetite. In homogeneous magnetic fields with an intensity of up to 0.4 T, the shear modulus of the composites was abnormally high (up to 10 000%). The variation of elastic properties of new materials on the type and volume content of the magnetic filler was investigated. In the presence of a sufficiently strong magnetic field, the above composites were shown to behave as elastoplastic materials with strengthening.

Stoichiometric polyelectrolyte complexes of ionic block copolymers and oppositely charged polyions.

Micellization in dilute solutions of diblock copolymers with a polyelectrolyte and a hydrophilic nonionic blocks and oppositely charged polyions is studied using mean-field theory. In aqueous solutions the micelle core consists of the polyelectrolyte complex (PEC) while the corona is formed by hydrophilic blocks of the block copolymers. Describing PEC as a globule in the framework of the Lifshitz [Zh. Eksp. Teor. Fiz. 55, 2408 (1968)] globule theory we calculate the surface tension of the micellar core/solvent interface as a function of the polyion degree of ionization, solvent quality, and concentration of low-molecular-mass salt. The equilibrium aggregation number of starlike micelles formed by block copolymers and homopolymers of opposite charge at stoichiometric mixture compositions is found as a function of the system parameters. It is shown that micelles disintegrate upon addition of salt.

Magnetic and viscoelastic response of elastomers with hard magnetic filler

Magnetic elastomers (MEs) based on a silicone matrix and magnetically hard NdFeB particles have been synthesized and their magnetic and viscoelastic properties have been studied depending on the size and concentration of magnetic particles and the magnetizing field. It has been shown that magnetic particles can rotate in soft polymer matrix under applied magnetic field, this fact leading to some features in both magnetic and viscoelastic properties. In the maximum magnetic field used magnetization of MEs with smaller particles is larger while the coercivity is smaller due to higher mobility of the particles within the polymer matrix. Viscoelastic behavior is characterized by long relaxation times due to restructuring of the magnetic filler under the influence of an applied mechanical force and magnetic interactions. The storage and loss moduli of magnetically hard elastomers grow significantly with magnetizing field. The magnetic response of the magnetized samples depends on the mutual orientation of the external magnetic field and the internal sample magnetization. Due to the particle rotation within the polymer matrix, the loss factor increases abruptly when the magnetic field is turned on in the opposite direction to the sample magnetization, further decreasing with time. Moduli versus field dependences have minimum at non-zero field and are characterized by a high asymmetry with respect to the field direction.

The Influence of Ion Pair Formation on the Phase Behavior of Polyelectrolyte Solutions

In this paper we calculate the phase diagrams of polyelectrolyte solutions taking into account the possibility of ion pair formation between counterions and ions on polymer chains with their subsequent aggregation in multiplets. Multiplets play a role of reversible physical crosslinks between different polymer chains. Furthermore, we assume that the dielectric constant, and hence the binding energy of ion pairs and multiplets, depends on the volume fraction of polymer in the solution. We have shown that ion pairing and multiplet formation leads to instability of the homogeneous phase, so that at some conditions the phase separation can proceed even in doog solvent. Another qualitatively new feature of the behavior of polyelectrolyte solutions is the emergence of a triple point on the phase diagram. The effect of the solvent polarity and the polarity of the dry polymer on the general form of the phase diagram is studied in detail.

Polyelectrolyte networks as highly sensitive polymers

This review presents the results of theoretical and experimental studies concerning collapse of polyelectrolyte gels. Along with classical investigations, a number of new effects are described; they are associated with the formation of ion pairs and with nonuniform distribution of low-molecular-mass counterions over the volume of the polyelectrolyte gel.

Stoichiometric polyelectrolyte complexes as comb copolymers

The collapse behavior of a single comblike copolymer chain has been studied by Monte Carlo simulations. It has been supposed that the solvent is good for the side chains but the solvent quality for the backbone chain changes. It has been shown that depending on the structural parameters of the comb copolymer (the lengths of the backbone and side chains, grafting density of the side chains) various thermodynamically stable morphologies of the collapsed backbone chain can be realized. In addition to ordinary spherical globule we have observed elongated structures as well as necklace-like conformations. The proposed model can be used to describe conformational behavior of stoichiometric complexes between block copolymers with a polyelectrolyte short block and oppositely charged linear homopolymers.

Micelle formation in a dilute solution of block copolymers with a polyelectrolyte block complexed with oppositely charged linear chains

The theory of micelle formation in a dilute solution mixture of polyelectrolyte/neutral diblock copolymers and oppositely charged linear chains has been developed. The core of the micelles is formed by the hydrophobic monomer units of polyelectrolyte complexes between the oppositely charged polyions while the hydrophilic uncharged blocks of the block copolymers comprise the micellar corona. The process of the formation of polyelectrolyte complexes and micelles in the solution has been described as sets of association–dissociation reactions with certain chemical constants and the concentration distribution of micellar aggregates of a given composition has been calculated for various concentrations of linear chains and block copolymer macromolecules in the solution. It was shown that the micelles are formed by nearly fully neutralized block copolymers, so that the micellar charge is close to zero. The aggregation number of the micelles and their charge slightly depend on the concentration of the block copol...

Magnetoactive elastomer based on magnetically hard filler: Synthesis and study of viscoelastic and damping properties

This work is focused on the magnetic response of magnetoactive elastomer (MAE) based on silicone polymer matrices filled with magnetic particles of magnetically hard NdFeB-alloy. Viscoelastic properties of MAE were studied by the method of oscillation shear. After magnetization in an external magnetic field of 2 T MAE samples demonstrate more than two-time increase in the storage and loss moduli and 25% increase in the loss factor. Performed study of the damping properties of the materials has shown that the oscillation time of the pendulum hammering the magnetized sample is in two times shorter than in case of the non-magnetized sample. Viscoelastic and damping properties of MAE are defined by magnetic interactions between the magnetized particles of the magnetic filler.

Low Frequency Rheology of Magnetically Controlled Elastomers with Isotropic Structure

The method of torsion oscillations is used to measure the dynamic modulus of elasticity of magnetically controlled elastomers that comprise silicone rubber and carbonyl iron in the low-frequency (up to 100 Hz) range. The samples are synthesized in the absence of a magnetic field; therefore, they have an isotropic structure. In the measurements, a constant magnetic field (up to 24 kA/m) is superimposed along the axis of forced torsion oscillations of the sample. A simple model of the rheological behavior of magnetically controlled elastomers is proposed; the problem of torsion oscillations of a cylindrical sample is solved. From the comparison with the experiment for the materials under study, we determine the coefficients of the theoretical model and the corrections to them, which are made because of variations in the rheology of magnetically controlled elastomers under the influence of a magnetic field. The derived relations make it possible to exclude artifacts and to adequately describe dependences of the storage and loss moduli on the frequency of mechanical loading and the strength of the applied magnetic field.