Can the glass transition in bulk polymers be modeled by percolation picture?

Recent observations (Eur. Phys. J. E 9, 135 (2002)) showed that the vitrification process, which sets in during the linear bulk methyl methacrylate (MMA) polymerization carried out below glass transition temperatures, can be modelled by static percolation picture. To generalize this observation for different kind of bulk linear or crosslinked polymers not enough data are present in the literature. To cover partly this deficit we studied the glass transition of MMA and styrene (Sty) crosslinking copolymerization in varying ratios of MMA and Sty. Both the fluorescence intensity I and the lifetime of pyrene (Py) used as a nanosecond in situ fluoroprobe were monitored during the gelation time. Both I and increase dramatically as a result of the reduced mobility of the probes trapped in the glassy regions, appearing near the glass transition point. The average size of the glassy regions just below, and the strength of the infinite network formed upon the connection of the glassy regions above the glass transition point obey power law relations. The data around were interpreted on the basis of the percolation theory and we observed that the corresponding exponents and give static percolation values independent of the polymer composition.Received: 9 July 2004, Published online: 1 October 2004PACS: 64.60.Ak Renormalization-group, fractal, and percolation studies of phase transitions - 64.70.Pf Glass transitions - 82.35.Jk Copolymers, phase transitions, structure     

Third harmonics of the AC magnetic susceptibility: a method for the study of flux dynamics in high temperature superconductors

The temperature dependence of the 1st and 3rd harmonics ( ) of the AC magnetic susceptibility has been measured on melt grown YBCO samples for different frequencies and amplitudes of the AC magnetic field and intensity of a contemporaneously applied DC field. With the help of critical state models and of numerical simulations [22], we have devised a novel method, based on the combined analysis of the 1st and the 3rd harmonics (specifically on the comparison between and ), that allows to distinguish different temperature ranges dominated by the different dissipative magnetic flux regimes. In particular, we identified three principal zones in the temperature dependence of the real part of the 3rd harmonic: the zone 1, in the temperature range below the peak of the imaginary part of the 1st harmonic, , and the zone 2, characterized by negative values in a temperature region just above , both dominated by the creep regime; the zone 3, just below T _c , in which we revealed the presence of Thermally Assisted Flux Flow (TAFF). By the identification of these zones, an estimation of the value of the pinning potential can be obtained.Received: 23 September 2003, Published online: 19 November 2003PACS: 74.25.Ha Magnetic properties - 74.60.Ge Flux pinning, flux creep, and flux-line lattice dynamics     

Dynamics of living polymers

We study theoretically the dynamics of living polymers which can add and subtract monomer units at their live chain ends. The classic example is ionic living polymerization. In equilibrium, a delicate balance is maintained in which each initiated chain has a very small negative average growth rate (velocity) just sufficient to negate the effect of growth rate fluctuations. This leads to an exponential molecular weight distribution (MWD) with mean . After a small perturbation of relative amplitude , e.g. a small temperature jump, this balance is destroyed: the velocity acquires a boost greatly exceeding its tiny equilibrium value. For the response has 3 stages: (1) Coherent chain growth or shrinkage, leaving a highly non-linear hole or peak in the MWD at small chain lengths. During this episode, lasting time , the MWDs first moment and monomer concentration m relax very close to equilibrium. (2) Hole-filling (or peak decay) after . The absence or surfeit of small chains is erased. (3) Global MWD shape relaxation after . By this time second and higher MWD moments have relaxed. During episodes (2) and (3) the fast variables ( ) are enslaved to the slowly varying number of free initiators (chains of zero length). Thus fast variables are quasi-statically fine-tuned to equilibrium. The outstanding feature of these dynamics is their ultrasensitivity: despite the perturbations linearity, the response is non-linear until the late episode (3). For very small perturbations, , response remains non-linear but with a less dramatic peak or hole during episode (1). Our predictions are in agreement with viscosity measurements on the most widely studied system, -methylstyrene.Received: 23 September 2003PACS: 82.35.-x Polymers: properties; reactions; polymerization - 05.40.-a Fluctuation phenomena, random processes, noise, and Brownian Motion - 87.15.Rn Biomolecules: structure and physical properties; Reactions and kinetics; polymerization     

Blobs,channels and “cigars”: Morphologies of liquids at a step

We have studied the equilibria of liquid droplets wetting a step edge with an opening angle by a combination of analytical and numerical methods. Depending on the wetting properties of the substrate walls and on the liquid volume, different locally or globally stable liquid morphologies are found. Complete spreading of the liquid along the bottom edge of the step is observed at equilibrium contact angles satisfying . If the contact angle exceeds a threshold value the liquid exists in a blob-like configuration. Surprisingly, we find an intermediate regime at a sufficiently high liquid volume and in a range of contact angles , in which cigar-shaped configurations arise in addition to the blob. We close the paper by a detailed discussion of the stability of this novel liquid morphology.PACS: 47.55.Dz Drops and bubbles - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 68.08.Bc Wetting     

Mechanical properties of mono-domain side chain nematic elastomers

We investigate the behavior of the shear rigidity modulus G = G + iG of three mono-domain side chain liquid-crystalline elastomers composed of side chain polysiloxanes cross-linked by either flexible or rigid cross-linkers. The measurements were taken in a frequency domain ranging form Hz to Hz applying the shear in a plane perpendicular to or containing the director. The measurements as a function of temperature show an anisotropy of G which appears around , when decreasing the temperature, and which is due to the expected lowering of coming from the coupling between the shear and the director. The measurements as a function of frequency show that G has two components for both geometries, in both the isotropic phase and in the nematic phase around the phase transition. One reflects the network behavior in its hydrodynamic regime (G is constant and , where f is the frequency), the other which appears at higher frequencies is characterized by a scaling law behavior ( ) of the Rouse type. We discuss the results in the framework of available theories and show that the three elastomers present a non-soft behavior, even for the elastomer for which the contrary was claimed, and that there is no separation of time scales between the director and the network. We also present data on a poly-domain sample and a non-mesomorphic one which complement these results.Received: 19 February 2004, Published online: 24 August 2004PACS: 83.80.Va Elastomeric polymers - 61.30.-v Liquid crystals - 83.60.Bc Linear viscoelasticityPresented at the First World Congress on Biomimetics and Artificial Muscles, 9-11 December 2002, Albuquerque, New Mexico, USA. Some aspects of this work have been published as an abridged version in the Proceedings of the Conference.     

БЕТАТРОННЫЕ КОЛЕБАН ИЯ В УСКОРИТЕЛЕ С ОБЩИМ ПОЛЕМ I

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Betatron oscillations in an accelerator with a general field I

The paper gives a linear theory of equilibrium trajectories in an accelerator with a generalized magnetostatic field, the components of which are defined on a general rotation surface. Equations of motion of the particles in natural coordinates are derived with respect to the change in energy and dissipative force. A system of equilibrium trajectories is found in the general form. Conditions for the field components on the reference surface, necessary for the existence of equilibrium trajectories, for the conservation of their geometric similarities and for maintaining the constancy of the frequencies of the betatron oscillations, are derived. A condition is also derived which must be satisfied by the reference surface in order to conserve constant circular frequency of the particles. It is seen that it is not possible to find a field for an accelerator with an exactly constant circular frequency and with constant frequencies of the betatron oscillation in the relativistic energy region. An ultra-relativistic cyclotron with such properties is realizable.

     

Phase chirality and stereo-selective swelling of cholesteric elastomers

Cholesteric elastomers possess a macroscopic phase chirality as the director rotates in a helical fashion along an optical axis z and can be described by a chiral order parameter . This parameter can be tuned by changing the helix pitch p and the elastic properties of the network at formation. The cholesterics also possess a local nematic order, changing with temperature or during solvent swelling. In this paper, by measuring the power of optical rotation , we discover how these two parameters vary as functions of temperature or solvent adsorbed by the network. The main result is a finding of pronounced stereo-selectivity of cholesteric elastomers, demonstrating itself in the retention of the correct chirality component of a racemic solvent. It has been possible to quantify the amount of such stereo-separation, and the basic dynamics of the effect.Received: 18 August 2003, Published online: 5 February 2004PACS: 33.55.Ad Optical activity, optical rotation; circular dichroism - 61.30.Vx Polymer liquid crystals - 87.80.Pa Morphometry and stereology     

Quasi-free \pi^0 photoproduction from the bound nucleon

Differential cross-sections for quasi-free photoproduction from the proton and neutron bound in the deuteron have been measured for MeV at using the Glasgow photon tagger at MAMI, the Mainz 48 cm cm NaI(Tl) photon detector and the Göttingen SENECA recoil detector. For the proton measurements made with both liquid-deuterium and liquid-hydrogen targets allow direct comparison of free photoproduction cross-sections as extracted from the bound-proton data with experimental free cross-sections which are found to be in reasonable agreement below 320 MeV. At higher energies the free cross-sections extracted from quasi-free data are significantly smaller than the experimental free cross-sections and theoretical predictions based on multipole analysis. For the first time, free neutron cross-section have been extracted in the -region. They are also in agreement with the predictions from multipole analysis up to 320 MeV and significantly smaller at higher photon energies.Received: 28 May 2003, Published online: 27 January 2004PACS: 13.60.Le Meson production - 14.20.Dh Protons and neutrons - 25.20.Lj Photoproduction reactionsK. Kossert: Part of the Doctoral Thesis.,Present address: Physikalisch-Technische Bundesanstalt, Bundesallee 100, D-38116 Braunschweig, Germany.Present address F. Wissmann: Physikalisch-Technische Bundesanstalt, Bundesallee 100, D-38116 Braunschweig, Germany. Present address B. Seitz: II. Physikalisches Institut der Universität Gießen, Germany.     

Exact effective force between star-polymers in a $\Theta$-solvent

We re-examine here the computation of the effective force between two star-polymers of respective numbers of branches f₁ and f₂, immersed in a common -solvent. Such a force originates essentially from the repulsive three-body interactions. To achieve this, we take advantage of some established results using renormalization theory for three-dimensional star-polymers, or conformal invariance for two-dimensional ones. We first show that, in dimension d = 3, the force, , decreases with the center-to-center distance r as , with the exact universal amplitude . Second, in dimension d = 2, we find that the force decays more slowly as , with the exact universal amplitude . For high distances compared to the gyration radius, , of a single polymer chain at the -point, an exponential decay of the force is expected.Received: 3 February 2004, Published online: 24 May 2004PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 05.20.-y Classical statistical mechanics     

О взаимодействии экс итонов с колебаниями кристаллической реш етки

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Influence of Solvent Polarity and Viscosity on Nonradiative Processes in Oligothiophenes with Intramolecular Charge Transfer

By the methods of luminescence, picosecond spectroscopy, and quantumchemical calculations the mechanisms of electron excitation energy deactivation in some oligothiophenes with intramolecular charge transfer depending on the solvent polarity and viscosity have been investigated. While for 2Npiperidino5(2,2dicyanovinyl)thiophene (PDCVT) the main channel of nonradiative deactivation is the transition to a lower intermediate state with a twisted double bond controlled by the medium viscosity, in the case of (E){2[25piperidino2thienyl]6(trifluoridemethyl)4H4pyranylidene}propanedinitryl (PTFDN) fluorescence quenching is initiated by the solvent polarity. For two other oligothiophenes, 2Npiperidino5cyanothiophene (PCT) and 2Npiperidino5cyanoterthiophene (PCTT), differing in the length of the thiophene chain, we have revealed, along with the effective quenching of fluorescence in shortchain PCT (independent of the solvent polarity and viscosity), an increase in the radiation capacity in PCTT with increasing polarity of the solvent. The possible mechanisms of nonradiative deactivation in the investigated oligothiophenes are discussed.     

Molecular dynamics in nanophase-separated comb-like poly( $ \upalpha$- n-alkyl $ \upbeta$-L-aspartate)s

A series of poly( -n-alkyl -L-aspartates) which are nanophase self-assembled comb-like polymers has been studied by dielectric spectroscopy in a broad frequency range ( 10^-23×10⁶ Hz), with n-alkyls side chains of various lengths, 10n18. In every member of the series the same relaxations were identified after the decomposition of the experimental isothermal trace in up to three peaks with relaxation times distributions. The strength, width and average relaxation time for all the relaxation modes were determined for each material. Besides the local low temperature, Arrhenius modes, two relaxation modes, and , present a cooperative character whose dynamics are not affected by the side chains melting. The relaxation is a polyethylene-like glass transition of the amorphous side chains and its dynamics is strongly dependent on the n value due to the increasing restrictions imposed by the self-assembled confinement. The strength of the relaxation mode increases as the lateral chains loose their 2D order. The restricted chopstick motion of the rigid rods is thought to be the origin of the mode; this motion is hindered at temperatures where the cage size decreases as a result of the increasing disorder with temperature.     

Twist-3 distribution amplitudes of the pion and kaon from the QCD sum rules

Twist-3 distribution amplitudes of the pion and kaon are studied in this paper. We calculate the first several moments for the twist-3 distribution amplitudes ( and ) of the pion and kaon by applying the QCD sum rules. Our results show that (i) the first three moments of and the first two moments of and of the pion and kaon can be obtained with 30 uncertainty; (ii) the fourth moment of the and the second moment of the can be obtained when the uncertainty are relaxed to 35 ; (iii) the fourth moment of the can be obtained only when the uncertainty are relaxed to 40 ; (iv) we have and after including the -corrections to the perturbative part. These moments will be helpful for constructing the twist-3 wave functions of the pion and kaon.Received: 6 January 2005, Revised: 29 March 2005, Published online: 22 June 2005PACS: 13.20.He, 11.55.Hx     

Double quantum transitions in paramagnetic resonance

The theory of double quantum transitions of the M=±2 type, with regard to inhomogeneously broadened spin systems is studied in this paper with the approximation ²T₂T₃ 1. We suppose that the inhomogeneous broadening is formed by an inhomogeneous crystal field. The obtained results describe the magnitude of absorption as a function of the h.f. power and also describe the shape of the absorption curve. It is demonstrated that in inhomogeneously broadened spin systems the absorption curve of double quantum transitions has the form of the difference of two different Lorentz's curves and that at the saturation ( ²T₂T₁ 1) the absorption increases with the cube of the h.f. field intensity. The shape of the curves is expressed by means of phenomenological relaxation constants of the system.

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M=±2 ²T₂T₃ 1. , - . . , ( ²T₂T₁ 1) . .

     

Paramagnetic resonance of Fe3+ ion in CdWO4 monocrystal

The paramagnetic spectrum of the Fe³⁺ ion in a CdWO₄ monocrystal was measured on a frequency of 9600 kMHz at 290°K. The spin-Hamiltonian of the Fe³⁺ ion was determined and had the form of (1). The constants derived for the spin-Hamiltonian areE/D=0·144±0·002,D=23·8 kMHz.

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Fe³⁺ CdWO₄

Fe³⁺ CdWO₄ 9600 kMHz 290°K. - Fe³⁺ (1), E/D 0,144±0,002 D 23,8 kMHz.

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In conclusion, the authors thank . Bárta and V. Kment from the Society for Chemical and Metallurgical Production in Ústí n/L for producing and supplying the monocrystals and for much valuable advice.     

Power law polydispersity and fractal structure of hyperbranched polymers

Using the complementary approaches of Flory theory and the overlap function, we study the molecular weight distribution and conformation of hyperbranched polymers formed by the melt polycondensation of A-R_N0-B_{f - 1} monomers in their reaction bath close to the mean field gel point p_A = 1, where p_A is the fraction of reacted A groups. Here , N₀ is the degree of polymerisation of the linear spacer linking the A group and the f-1 B groups and condensation occurs exclusively between the A and B groups. For , we assume that the number density of hyperbranched polymers with degree of polymerisation N generally obeys the scaling form and we explicitly show that this scaling assumption is correct in the mean field regime (here N_l is the largest characteristic degree of polymerisation and the function cuts off the power law sharply for ). We find the upper critical dimension for this system is d_c = 4, so that for the mean field values for the polydispersity exponent and fractal dimension apply: , d_f = 4. For d = 3, mean field theory is still correct for where is the Ginzburg point; for , mean field theory applies on small mass scales N<N_c but breaks down on larger mass scales N>N_c where is a cross-over mass. Within the Ginzburg zone (i.e., d<d_c, ), we show that the hyperbranched chains on mass scales N>N_c are non-Gaussian with fractal dimension given by d_f = d (for d = 2,3,4). Our results are qualitatively different from those of the percolation model and indicate that the polycondensation of AB_f-1, unlike polymer gelation, is not described by percolation theory. Instead many of our results are similar to those for a monodisperse melt of randomly branched polymers, a consequence of the fact that so that polydispersity is irrelevant for excluded volume screening in hyperbranched polymer melts.Received: 15 December 2003, Published online: 2 March 2004PACS: 82.35.-x Polymers: properties; reactions; polymerization - 05.70.Jk Critical point phenomena     

Monte Carlo simulation of particle aggregation and gelation: II. Pair correlation function and structure factor

Diffusion-limited cluster aggregation and gelation are studied using lattice and off-lattice Monte Carlo simulations. The pair correlation function g(r) and the structure factor S(q) of the particle gels were investigated as a function of the volume fraction ( ) and time. At volume fractions below , the gel structure is fractal on small length scales with . g(r) shows a weak minimum at the correlation length ( ), before reaching the average concentration at large length scales. The cut-off function of g(r) varies during the aggregation process, but at a given , where is the gel time, it is a universal function of . At high volume fractions, the structure is dominated by excluded-volume interactions, while at low volume fractions, it is determined by the connectivity.Received: 27 April 2004, Published online: 26 October 2004PACS: 64.60.Ak Renormalization-group, fractal, and percolation studies of phase transitions - 02.70.Uu Applications of Monte Carlo methods     

The distribution of neutron density in the vicinity of a partly inserted black rod in two-group approximation

The neutron density in the vicinity of a black cylindrical rod partly inserted in a bare reactor is calculated and illustrated by a numerical example. The starting point is a two-group diffusion theory approximation. While the dependence of the effect of the rod on the insertion depth can be calculated simply by means of perturbation theory, the question of the neutron density estimate in the vicinity of the rod is considerably more difficult and in some considerations the estimate of the neutron density caused by the presence of the rod is indispensable. The method makes it possible to determine the reactivity value of the rod in dependence on the insertion depth and especially the neutron density deformation in the vicinity of the rod.

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In conclusion the author thanks J. Svato for help in carrying out the numerical calculations.     

The Gelfand-Levitan equation and its application to the scattering of neutrons on protons

The Gelfand-Levitan equation for the kernelP(r, r) (withrr) is formulated and then applied for determining the scattering potential in the scattering of slow neutrons on protons (for the case when the dependence of the nuclear forces on the spins can be neglected and onlys-scattering need be considered). The potentials obtained are the same as the Bargmann ones, found by a different method.

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-

- P(r, r) ( rr). , ( s- ). , .

     

ИЗЛУЧЕНИЕ ЧЕРЕНКОВА ПРОСТРАНСТВЕННОГО З АРЯДА В ВОЛНОВОДАХ И В НЕОГР АНИЧЕННОЙ СРЕДЕ

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