Depletion effect on partial organization of atactic polymer chain segments in microcells

Glass transition for atactic poly(methyl methacrylate) (a-PMMA) prepared in nano-cells by microemulsion polymerization was measured at a faster heating rate after slow cooling of the sample from a temperature above T_g. An additional enthalpy relaxation and glass transition were observed at higher temperatures for the a-PMMA sample due to the partial organization of the chain segments which occurred during microemulsion polymerization. The re-precipitated a-PMMA did not show any self-organization under the same thermal conditions, although there are no changes in molecular weight or tacticity of the polymer chains. A depletion-interaction phenomenon was understood to provide entropic force for the self-organization of polymer chains inside the walls of the microemulsion cells.     

Ion crater healing and variable temperature ellipsometry as complementary probes for the glass transition in thin polymer films

Poly(methyl methacrylate) (PMMA) thin films of various tacticity and thickness were bombarded at grazing angles by 20 MeV Au ions at different temperatures. The shape of the tracks was investigated by scanning force microscopy (SFM) after annealing for various time at different temperatures and constant quenching rate. The thickness dependent glass transition temperature, T(g)(h), was estimated from the temperature of relaxation of ion-caused nanodeformations in the films. T(g)(h) obtained from the thermal healing of the holes and hillocks is found in good agreement with the one determined by variable temperature ellipsometry for PMMA film thickness of 80 nm and corresponds to the T(g) of each bulk PMMA stereoisomer. Below this thickness, some significant divergences are observed between the T(g) measured by the two techniques. We propose that the healing of ion crater hillock and the kink in the thermal expansion arise from the different nature of chains motions which are perturbed to different extents according to the main polymer chain preferential orientation in the thin film. This can be tentatively interpreted by a so-called "anisotropic" character of the glass transition.     

Dynamics of water in molecular sieves by dielectric spectroscopy

We present recent dielectric data on the dynamics of water confined in molecular sieves with pore sizes 5 and 10 A. The dielectric measurements in the frequency and temperature ranges 10(-2)-10(6) Hz and 120-300 K show three relaxation processes for both samples. In the case of the 10 A pore the slowest process shows an Arrhenius temperature dependence at low temperatures (<220 K), while at high temperatures the relaxation appears to follow a more Vogel-Fulcher-Tammann (VFT) like behaviour. The relaxation time for this process is 100 s at about 170 K. The second slowest process is at low temperatures very similar to the main process of (bulk-like) water in a fully hydrated clay, but also this process seems to exhibit some kind of dynamical transition, in this case at T approximately 185 K. All the three processes in the 5 A pore exhibit Arrhenius temperature dependence, and two of them are considerably slower than the main relaxation in the hydrated clay. Thus, dynamics of bulk-like water is only observed in the 10 A molecular sieves, and most of the water molecules in both 5 and 10 A pores have considerably slower dielectric relaxation than has been observed for water confined in clay, most likely due to strong interactions with the considerably more hydrophilic inner surfaces of molecular sieves.     

Dynamic-susceptibility studies of the interplay between the Néel and Brown magnetic relaxation mechanisms

We have used temperature- and frequency-resolved ac-susceptibility measurements to investigate the magnetic relaxation of a Co_0.2Fe_2.8O₄ magnetic fluid above the freezing point of the liquid carrier. Our data show that both the Néel and the Brown relaxation mechanisms are operative at temperatures in the vicinity of the out-of-phase (imaginary) susceptibility peak. We separate the contributions of the two mechanisms to the overall relaxation time, and demonstrate that Brownian relaxation plays a dominant role at all temperatures within this high-dissipation regime.     

TSDC studies of the effects of plasticizer and water on the sub-T g relaxations of an epoxy resin system

The sub-glass-transition-temperature (sub-T _g relaxations of an epoxy resin system based on diglycidyl ether of bisphenol-A (DGEBA) and cured with triethylenetetramine (TETA) were investigated by means of the thermally stimulated depolarization current (TSDC) technique in the temperature range 77 K to 300 K. Three relaxation regions were observed: the γ relaxation at about 150 K, the β relaxation at 160 K to 200 K and the ω relaxation at 240 K to 270 K. The plasticization effect on the aforementioned relaxations of a plasticizer chemically connected to the epoxy resin network was investigated. The amount of plasticizer (commercial name THIOCOL LP3) was varied between 0% and 60% by weight of the epoxy. The broad range of the β relaxation reflects the heterogeneous structure of the material. The activation energies of the γ and β relaxations were calculated using the thermal sampling technique. Physical aging strongly influenced the TSDC thermogram of the ω relaxation, indicating phase separation during the aging procedure. Water effects were systematically investigated from dry samples to water-saturated samples (water content, 2.5%). In all specimens, water induced plasticization, which is expressed by the shifting of the β relaxation toward lower temperatures. The mode of water absorption (immersion in water or exposure to humid environment) also influenced the evolution of the ω relaxation.     

Brillouin scattering in liquid sulfur dioxide: relaxational behaviour

The frequency dependence of hypersonic absorption and the dispersion of hypersonic speed in liquid sulfur dioxide (SO₂) were determined at (293.75±0.30) K and at (284.65±0.30) K by Brillouin spectroscopy. The results are used to experimentally establish the second relaxation step in the double vibrational relaxation of these quantities in the liquid phase, which was first conjectured by R. Bass and J. Lamb, Proc. R. Soc. Ser. A (1958) 243, 94. This second relaxation takes place at approximately 1.5 GHz for both temperatures within experimental error, whereas the first relaxation step, previously determined by ultrasonic spectroscopy, takes place at approximately 23 MHz. In the course of this investigation, some evidence was found that for the temperatures considered the shear viscosity relaxes in the hypersonic frequency range.     

Shear modulus of polydomain, mono-domain and non-mesomorphic side-chain elastomers: Influence of the nematic order

We investigate the behavior of the complex shear modulus of a series of elastomers including mono-domain and poly-domain liquid crystal samples, and a non-mesomorphic sample. We find that the dynamics of the glass transition are strongly modified by the nematic order. This result explains why the truly elastic response of liquid crystal elastomers can only be observed in the isotropic phase at very high temperatures and at very low frequencies. Between the elastic regime and the glassy state, the elastomers have a visco-elastic regime, which is characterized by a Rouse-like behavior for mono-domain and poly-domain samples, and by a Zimm-like behavior for the non-mesomorphic sample. We also show that the mono-domain sample exhibits marked anisotropy of the shear-modulus G ^′. This anisotropy, which is observed for the first time, is a function of frequency and is inverted between low and high frequencies, due to relaxation effects of the orientational order. Received 28 January 2000 and Received in final form 16 October 2000     

Evidence of internal protein dynamics in transferrins from TDPAC experiments

The relaxation in liquid transferrin and ovotransferrin samples has been studied at different temperatures using the TDPAC method. Information about reorientation and internal dynamics has been obtained from immobilized protein samples. Characteristic differences between the two proteins will be discussed.     

Amorphous linear polyethylene: Annealing effects

The effect of annealing amorphous linear polyethylene films prepared by an improved ultraquenching technique at temperatures just below and above a dynamic mechanical relaxation peak (torsion braid) observed at ∽190K has been characterized by electron microscopy and torsion braid analysis. Based on the results described, this peak is believed related to the lower glass transition temperature T_g(L), the T_g of wholly amorphous linear polyethylene, whereas the β peak at 260K is T_g (upper). Annealing just below T_g (L) results in a growth in size of the nodules observed in the as-quenched samples, whereas annealing above T_g (L) can result in the growth of single crystal-like structures, spherulites, and shish-kebobs. Storage of the crystallized samples at room temperatures results in a decrease in size of the relaxation peak during subsequent torsion braid spectroscopy measurements. The results indicate significant amounts of molecular motion can occur during crystallization even at T_g.     

Effect of Mo3+ ions on Nd3+ spin-lattice relaxation in Y3Al5O12

The content of Mo³⁺ ions in YAG:Nd garnet samples prepared by different technologies has been studied, and the spin-lattice relaxation rate of these ions at temperatures of 4–5 K measured. It is concluded is drawn that Mo³⁺ ions can play the part of rapidly relaxing centers mediating the Nd³⁺ spin-lattice relaxation at liquid-helium temperatures. This may account for a number of features in the spin-lattice relaxation of rare-earth ions in garnets, observed earlier at low temperatures. Fiz. Tverd. Tela (St. Petersburg) 40, 2026–2028 (November 1998)     

Frequency-dependent loss in amorphous semiconductors

Recent developments in the theoretical analysis and experimental study of frequency-dependent loss by relaxation in amorphous semiconductors are reviewed. A unified theoretical treatment of the complex a.c. conductivity is given, within the pair approximation, for single electron tunnelling and hopping in both uncorrelated and strongly correlated cases, and the discussion is then extended to pair processes and to atomic relaxation. The problems associated with measuring the frequency dependent conductivity of amorphous samples are considered, and relevant measurements reported for the different classes of amorphous semiconductors, tetrahedral and group V materials and chalcogenides are reviewed in the light of the available theoretical models. The similarity in the magnitudes and frequency, temperature and electric field dependences of the losses observed in many different systems at liquid helium temperatures is noted, and the possible physical reasons for this are examined.     

The holographic investigation of diffusion of azo-dye in liquid crystals host

The diffusion of azo-dye (DR-1) in a planar liquid crystals host (5CB) at various temperatures has been investigated by laser-induced holographic grating relaxation technique. The decay of the diffraction intensity provides information about the diffusion of photoexcited azo-dye molecules. The relaxation time constants can be derived from the time dependence of the diffraction intensity fitted by a single exponential function. Thus, the diffusion coefficients parallel and perpendicular to the director of liquid crystals at various temperatures can be obtained from the plots of the reciprocal of the relaxation time versus the square of the grating vector. From the analysis of the holographic grating relaxation, the diffusion is faster along the molecular director than for the perpendicular case, and the diffusion increases with rising temperature either parallel or perpendicular to the nematic director of liquid crystals. PACS 42.40.Eq; 42.40.Lx     

Mechanical relaxation of single crystal mats of polyethylene in a crystalline dispersion region

Stress-relaxation measurements have been conducted over the temperature range 15°–105°C on mats of single crystals of two linear polyethylene fractions. The single crystals were grown isothermally at several different temperatures. The relaxation modulus was observed to be strain dependent, indicating that the single crystal mats exhibited nonlinearity.

In spite of this appearance of nonlinearity, it was found possible, when the relaxation modulus was extrapolated to zero strain by an appropriate method, to obtain correct relaxation spectra for the mats of single crystals prepared by isothermal crystallization. This spectrum was then used to calculate the dynamic viscoelastic functions and, for the unannealed sample crystallized at 80°C, good agreement was found between experimental results and calculated ones. Two annealed samples showed multiple absorptions and, under these circumstances, strict application of the method of reduced variables for time and temperature was impractical.

The effect of molecular weight on the intensity of the relaxation spectrum was investigated. It was found that the single crystal with the higher molecular weight showed an increased spectrum intensity.

Observations were also made of the effect of increased lamellar thickness on both the relaxation spectra and the dynamic complex moduli and the results obtained on the fractions studied were compared with prior studies in whole polymer.     

Hyperfine interactions in amorphous Tm-Cu Alloys

Hyperfine interactions in sputtered amorphous Tm_xCu_1?x, with x=0.70, 0.50, and 0.33, have been measured over a temperature range from 1.7 K to room temperature using the Mössbauer effect in¹⁶⁹Tm. At low temperatures each spectrum shows a well resolved six-line hyperfine pattern indicative of magnetic order and a superimposed quadrupole doublet. The relative spectral weight of the magnetic component increases with increasing Tm concentration and decreases with increasing temperature. The magnetic component persists at unexpectedly high, temperatures with no decrease in overall splitting and no evidence of electronic relaxation. For all three concentrations, the magnetic splitting is the same as that of Tm metal at low temperatures, nearly the free-ion limit. The electric quadrupole shift of the magnetic component is the same for the three samples, but is significantly less than that of Tm metal (hexagonal) and much larger than that of crystalline TmCu (cubic). The non-magnetic doublets have quadrupole splittings that are very nearly the same for the three concentrations and show considerable asymmetry, a typical effect of electronic relaxation, which persists at temperatures above where the magnetic component disappears.     

Ion crater healing and variable temperature ellipsometry as complementary probes for the glass transition in thin polymer films

The European Physical Journal E - Poly(methyl methacrylate) (PMMA) thin films of various tacticity and thickness were bombarded at grazing angles by 20 MeV Au ions at different temperatures. The...     

Electron paramagnetic relaxation in aqueous solutions of manganese (II) ions

The processes of the electron paramagnetic relaxation, molecular motions and structural changes in aqueous solutions of manganese nitrate have been investigated by direct measurement of spin-lattice (T ₁) and spin-spin (T ₂) relaxation times for a wide range of concentrations, temperatures and viscosities. T ₁ and T ₂ were measured by a non-resonance absorption method.

It was discovered that some structural regions exist at the different concentrations of Mn(II) ions in solution. So, the structure of highly concentrated solutions may be considered as one of the corresponding crystallohydrate. The structural microinhomogeneities were observed also in the intermediate concentration range at definite temperatures. It is shown that the relaxation mechanism proposed by Bloembergen and Morgan is not effective in the concentration range studied by us.

The analysis of relaxation times and E.P.R. spectra has shown the formation of ‘liquid microphases’ at the freezing point of the solution. Such microphases can exist at temperatures a few tenths of a degree below the solvent freezing point, and its composition considerably differs from the initial solution.

The correlation times for intramolecular and intermolecular electron relaxation mechanisms are evaluated and their nature is discussed.     

NMR study of the dynamics of 3He impurities in the proposed supersolid state of solid 4He

The dynamics of (3)He atoms in solid (4)He have been investigated by measuring the NMR relaxation times T(1) and T(2) in the region where a significant nonclassical rotational inertia fraction has been reported. For (3)He concentrations x(3)=16 and 24 ppm, changes are observed for both the spin-lattice relaxation time T(1) and the spin-spin relaxation time T(2) at the temperatures corresponding to the onset of the nonclassical rotational inertia fraction and, at lower temperatures, to the (3)He-(4)He phase separation. The magnitudes of T(1) and T(2) at temperatures above the phase separation agree roughly with existing theory based on the tunneling of (3)He impurities in the elastic strain field due to isotopic mismatch. However, a distinct peak in T(1) and a less well-resolved feature in T(2) are observed near the reported nonclassical rotational inertia fraction onset temperature, in contrast to the temperature-independent relaxation times predicted by the tunneling theory.     

An internal friction study of the vanadium-deuterium system

The internal friction of deuterium-doped vanadium has been investigated in the temperature range from 65 to 350 K. At low deuterium concentrations (≦0.18 at.−%) a relaxation effect has been observed near 90 K; its activation energy and its limiting relaxation tiem are 0.17 eV and 2×10⁻¹² sec, respectively. A second internal friction peak (precipitation peak) appears in more heavily doped samples; the position of this second peak shifts to higher temperatures as the deuterium content is increased. Possible mechanisms for the two peaks are discussed. The phase diagram of the vanadium-deuterium system at low temperatures has been deduced from the correlation between the deuterium concentration and the position of the precipitation peak.     

Kinetics of light scattering in an epoxy resin suspension of carbon microparticles

The relaxation kinetics of laser-induced scattering and absorption was investigated in a liquid epoxy resin suspension of carbon microparticles. The scattered light intensity and the optical transmittance at temperatures below +10°C demonstrate anomalous kinetics with a distinct build-up stage. The observed behavior is interpreted as a manifestation of processes of mechanical stress relaxation in epoxy layers around microbubbles. The microbubbles induced by laser irradiation of the suspension can be a tool for the investigation of mechanical stress relaxation in polymers.     

A comparison of effective and polarizable intermolecular potentials in simulations: liquid water as a test case

A comparison of polarizable and effective intermolecular potentials has been carried out by employing simulated properties of liquid water at different temperatures. The effective potentials were obtained by adding a fixed fraction (~80%) of the induced dipole moments of the polarizable potential to the permanent dipole moment of the water molecule. The fraction was fitted to reproduce one structural (the height of the first peak of the oxygen-oxygen radial distribution function) and one dynamic (the self-diffusion coefficient) liquid property predicted by the polarizable potential. The two properties were well reproduced simultaneously by the effective potential at 273 K and 303 K, but less accurately at 373 K. The effective dipole moments were 2.79, 2.75, and 2.68 D at the three respective temperatures. In order to examine the effective potentials further, other liquid properties have been considered, and we found that the molecular rotational relaxation times and the hydrogen bonding properties are reproduced well by the effective potentials, whereas the velocity autocorrelation function, the pressure, the dielectric constant, and the Debye relaxation time are reproduced less accurately.